[go: up one dir, main page]

EP3183757B1 - Composition à semi-conducteurs organiques comprenant un milieu liquide - Google Patents

Composition à semi-conducteurs organiques comprenant un milieu liquide Download PDF

Info

Publication number
EP3183757B1
EP3183757B1 EP15833336.9A EP15833336A EP3183757B1 EP 3183757 B1 EP3183757 B1 EP 3183757B1 EP 15833336 A EP15833336 A EP 15833336A EP 3183757 B1 EP3183757 B1 EP 3183757B1
Authority
EP
European Patent Office
Prior art keywords
bis
alkyl
perylene
dicarboximide
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15833336.9A
Other languages
German (de)
English (en)
Other versions
EP3183757A4 (fr
EP3183757A1 (fr
Inventor
Ilja AIZENBERG
Jochen Brill
Dieter Freyberg
Thomas Weitz
Thomas Musiol
Silke Annika KÖHLER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clap Co Ltd
Original Assignee
Clap Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clap Co Ltd filed Critical Clap Co Ltd
Publication of EP3183757A1 publication Critical patent/EP3183757A1/fr
Publication of EP3183757A4 publication Critical patent/EP3183757A4/fr
Application granted granted Critical
Publication of EP3183757B1 publication Critical patent/EP3183757B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the use of a semiconductor composition comprising at least one organic semiconductor in a liquid medium and to a process using said semiconductor composition for the production of organic semiconductor devices, in particular organic field-effect transistors, organic solar cells, light-emitting diodes and sensors.
  • Organic semiconductors based on low molecular weight molecules or polymeric materials are already used in many sectors of the electronics industry. In many cases, these organic semiconductors have advantages over the classical inorganic semiconductors, for example better substrate compatibility and better processability of the semiconductor components based on them. They allow processing on flexible substrates and enable their orbital energies to be adjusted precisely to the particular application range by the methods of molecular modeling. The significantly reduced costs of such components have brought an upswing to the field of research of organic electronics.
  • Organic electronics is concerned principally with the development of new materials and manufacturing processes for the production of electronic components based on organic semiconductor layers. These include in particular organic field-effect transistors (OFETs) and organic electroluminescent devices (hereinafter abbreviated as "EL" devices).
  • OFETs organic field-effect transistors
  • EL organic electroluminescent devices
  • An organic electroluminescent device is a self-emission device utilizing the principle that a fluorescent material emits light by the recombination energy of holes injected from an anode and electrons injected from a cathode when an electric field is applied.
  • OLEDs organic light-emitting diodes
  • cathode ray tubes and liquid-crystal displays for producing flat visual display units.
  • OLEDs organic light-emitting diodes
  • Organic photovoltaics is concerned principally with the development of new materials for organic solar cells.
  • a great potential for development is ascribed to materials which have maximum transport widths and high mobilities for light-induced excited states (high exciton diffusion lengths) and are thus advantageously suitable for use as an active material in so-called excitonic solar cells. It is generally possible with solar cells based on such materials to achieve very good quantum yields.
  • organic electronic devices organic solar cells and optoelectronic devices, such as organic thin film transistors (OTFTs), OLEDs, printable circuits, capacitors, sensors etc.
  • OFTs organic thin film transistors
  • OLEDs organic thin film transistors
  • printable circuits capacitors, sensors etc.
  • wet-processing techniques that allow the preparation of active components comprising organic semiconductors that good application properties (e.g. high charge carrier mobilities) and are stable under ambient conditions.
  • US 2014042369 A1 describes an organic semiconductor formulation comprising an organic semiconductor in a liquid medium, wherein the liquid medium comprises a first liquid and optionally a second liquid, the first liquid being an aromatic compound having electronic properties complementary to the electronic structure of the organic semiconductor compound, and the second liquid being a solvent or solvent mixture in which the organic semiconductor has a solubility of at least about 0.1 mg/mL.
  • the only semiconductor used in the working examples is N,N'-bis(2-ethylhexyl)-(1,7 and 1,6)-dicyanoperylene-3,4:9,10-bis(dicarboximide).
  • the tested solvents are N,N-dimethylaniline, nitrobenzene, 2-methylanisole, xylene, dichlorobenzene and benzonitrile.
  • US 4,678,608 A relates to compositions intended to be reacted with or activated by hydrogen peroxide in the presence of an organic solvent to produce chemiluminescent light, where the composition contains an oxalate, a fluorescer and a soluble perylene dye.
  • a suitable perylene dye is N,N'-bis(2,5-di-t-butylphenyl)-3,4,9,10-perylenedicarboximide.
  • Preferred organic solvents are dialkylphthalates, such as dibutylphthalate.
  • N,N-dimethylaniline and nitrobenzene are toxic and environmentally dangerous and 2-methylanisol, xylene, dichlorobenzene and benzonitrile are harmful to health.
  • liquid aliphatic or aromatic carbocycles and heterocycles that bear at least two carboxylic ester groups are particularly suitable for liquid organic semiconductor compositions. They are non-hazardous, show a good compatibility with a great number of different organic semiconductors and the resulting liquid organic semiconductor formulations are suitable for the production of various semiconductor devices with good application properties.
  • the use of said liquid aliphatic or aromatic carbocycles and heterocycles leads to the formation of thin films that exhibit excellent application properties in various field effect devices.
  • the liquid compositions according to the invention are especially suitable for the formation of organic thin film transistors (OTFTs) by a wet-processing technique under ambient conditions.
  • OFTs organic thin film transistors
  • the semiconductor layers obtained from the liquid compositions according to the invention are characterized by good solid state properties, e.g. a good crystallinity.
  • field-effect devices such as thin-film transistors that are fabricated with the semiconductor compositions usually have high performance under ambient conditions, e.g. characterized by one or more of the following properties: large charge mobilities, low threshold voltages, and high current on-off ratios.
  • a first object of the present invention relates to the use of a composition comprising
  • composition according to the invention additionally comprises a cosolvent C) selected from organic solvents and mixtures of organic solvents different from component B).
  • a further object of the invention is a process for the preparation of an electronic device, optical device or optoelectronic device, comprising:
  • a further object of the invention is the use of a composition as defined above and in the following for the production of a semiconductor material, preferably a semiconductor material in organic electronics or in organic photovoltaics.
  • devices comprising an organic semiconductor component prepared from a composition according to the invention can exhibit improved properties because the liquid component B) is beneficial for the deposition of the organic semiconductor A) on a substrate.
  • component B) shows an ideal balance of good solubility with respect to the semiconductors A) and a sufficient low volatility to allow the formation of semiconductor layers with excellent properties.
  • this leads to advantageous solid state properties, like the formation of larger crystallites and a reduced number of grain boundaries.
  • An increase in crystallinity, crystal grain size and crystalline domains of semiconductor layers deposited from a composition according to the invention can be detected by optical microscopy (see figs. 1a and 1b ). Larger crystallites can contribute, at least in part, to improved charge transport, possibly because of the reduced number of grain boundaries which act as charge trapping sites.
  • the present teachings provide organic semiconductor formulations that can exhibit properties such as tailored compatibility with a given organic semiconductor, improved long-term and chemical stability, low-temperature processability, and large processing versatility.
  • field effect devices such as thin film transistors that are fabricated with the present semiconductor formulations can have high performance under ambient conditions, for example, demonstrating one or more of large charge mobilities, low threshold voltages, and high current on-off ratios.
  • the new organic semiconductor composition has at least one of the following advantages:
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, particularly chlorine, bromide or iodine.
  • the expression "unsubstituted or substituted alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl” represents unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl.
  • the expression "unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino" represents unsubstituted or substituted alkyl, unsubstitute
  • alkyl comprises straight-chain or branched alkyl groups.
  • Alkyl is preferably C 1 -C 30 -alkyl, more preferably C 1 -C 22 -alkyl.
  • Short chain alkyl groups are preferably selected from C 1 -C 6 -alkyl groups.
  • Long chain alkyl groups are preferably selected from C 7 -C 22 -alkyl groups.
  • alkyl groups are especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 1-ethylpropyl, neo-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 2-ethylpentyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1-propylpentyl, 2-propylpentyl, n-nonyl, 1-methyloctyl
  • R a is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • alkyl groups whose carbon chains are interrupted by one or more nonadjacent groups are especially 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2-and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-triox
  • Substituted alkyl groups may, depending on the length of the alkyl chain, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO 3 H, sulfonate, sulfamino, sulfamide, amidino, NE 5 E 6 where E 5 and E 6 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • Cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents of the alkyl groups may in turn be unsubstituted or substituted; suitable substituents are the substituents mentioned below for these groups.
  • Special embodiments of substituted alkyl groups are perfluoro-C 1 -C 30 -alkyl, 1H,1H-perfluoro-C 2 -C 30 -alkyl and 1H,1H,2H,2H-perfluoro-C 3 -C 30 -alkyl. Examples for those fluorinated alkyl groups are mentioned in the following.
  • substituted alkyl groups are especially carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 8-carboxyoctyl, 10-carboxydecyl, 12-carboxydodecyl and 14-carboxy-tetradecyl; sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl; 2-hydroxyethyl, 2- and 3-hydroxypropyl, 1-hydroxyprop-2-yl, 3- and 4-hydroxybutyl, 1-hydroxybut-2-yl and 8-hydroxy-4-oxaoctyl;
  • Carboxylate and sulfonate respectively represent a derivative of a carboxylic acid function and a sulfonic acid function, especially a metal carboxylate or sulfonate, a carboxylic ester or sulfonic ester function or a carboxamide or sulfonamide function.
  • Such derivatives include, for example, esters with C 1 -C 4 -alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
  • alkoxy groups are especially methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert-pentoxy and hexoxy.
  • alkylthio groups are especially methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio and hexylthio.
  • Examples of monoalkylamino groups and dialkylamino groups are especially methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, pentylamino, hexylamino, dimethylamino, methylethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, dipentylamino, dihexylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, diphenylamino and dibenzylamino;
  • Alkylene represents a linear saturated hydrocarbon chain having from 1 to 10 and especially from 1 to 4 carbon atoms, such as ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl or hexane-1,6-diyl.
  • cycloalkyl denotes a mono-, bi- or tricyclic hydrocarbon radical having usually from 3 to 20, preferably 3 to 12, more preferably 5 to 12, carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl, norbornyl, bicyclo[2.2.2]octyl or adamantyl.
  • Substituted cycloalkyl groups may, depending on the ring size, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO 3 H, sulfonate, sulfamino, sulfamide, amidino, NE 7 E 8 where E 7 and E 8 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • the cycloalkyl groups preferably bear one or more, for example one, two, three, four or five, C 1 -C 6 -alkyl groups.
  • substituted cycloalkyl groups are especially 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 2-, 3- and 4-propylcyclohexyl, 2-, 3- and 4-isopropylcyclohexyl, 2-, 3-and 4-butylcyclohexyl, 2-, 3- and 4-sec.-butylcyclohexyl, 2-, 3- and 4-tert-butylcyclohexyl, 2-, 3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 2-, 3- and 4-propylcycloheptyl, 2-, 3- and 4-isopropylcycloheptyl,
  • aryl refers to mono- or polycyclic aromatic hydrocarbon radicals.
  • Aryl usually is an aromatic radical having 6 to 24 carbon atoms, preferably 6 to 20 carbon atoms, especially 6 to 14 carbon atoms as ring members.
  • Aryl is preferably phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl, perylenyl, etc., and more preferably phenyl or naphthyl.
  • Substituted aryls may, depending on the number and size of their ring systems, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO 3 H, sulfonate, sulfamino, sulfamide, amidino, NE 9 E 10 where E 9 and E 10 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents on the aryl may in turn be unsubstituted or substituted. Reference is made to the substituents mentioned above for these groups.
  • the substituents on the aryl are preferably selected from alkyl, alkoxy, haloalkyl, haloalkoxy, aryl, fluorine, chlorine, bromine, cyano and nitro.
  • Substituted aryl is more preferably substituted phenyl which generally bears 1, 2, 3, 4 or 5, preferably 1, 2 or 3, substituents.
  • Substituted aryl is preferably aryl substituted by at least one alkyl group ("alkaryl", also referred to hereinafter as alkylaryl).
  • Alkaryl groups may, depending on the size of the aromatic ring system, have one or more (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more than 9) alkyl substituents.
  • the alkyl substituents may be unsubstituted or substituted. In this regard, reference is made to the above statements regarding unsubstituted and substituted alkyl.
  • the alkaryl groups have exclusively unsubstituted alkyl substituents.
  • Alkaryl is preferably phenyl which bears 1, 2, 3, 4 or 5, preferably 1, 2 or 3, more preferably 1 or 2, alkyl substituents.
  • Aryl which bears one or more radicals is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3-
  • heterocycloalkyl comprises nonaromatic, unsaturated or fully saturated, cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms.
  • the heterocycloalkyl groups compared to the corresponding cycloalkyl groups, 1, 2, 3, 4 or more than 4 of the ring carbon atoms are replaced by heteroatoms or heteroatom-containing groups.
  • R b is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • heterocycloalkyl groups are especially pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, dihydrothien-2-yl, tetrahydrofuranyl, dihydrofuran-2-yl, tetrahydropyranyl, 2-oxazolinyl, 3-oxazolinyl, 4-oxazolinyl and dioxanyl.
  • Substituted heterocycloalkyl groups may, depending on the ring size, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO 3 H, sulfonate, sulfamino, sulfamide, amidino, NE 11 E 12 where E 11 and E 12 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • the heterocycloalkyl groups preferably bear one or more, for example one, two, three, four or five,
  • heteroaryl comprises heteroaromatic, mono- or polycyclic groups.
  • ring carbon atoms these have 1, 2, 3, 4 or more than 4 heteroatoms as ring members.
  • the heteroatoms are preferably selected from oxygen, nitrogen, selenium and sulfur.
  • the hetaryl groups have preferably 5 to 18, e.g. 5, 6, 8, 9, 10, 11, 12, 13 or 14, ring atoms.
  • Monocyclic hetaryl groups are preferably 5- or 6-membered hetaryl groups, such as 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2-thienyl (thiophen-2-yl), 3-thienyl (thiophen-3-yl), selenophen-2-yl, selenophen-3-yl, 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, pyrrol-1-yl, imidazol-2-yl, imidazol-1-yl, imidazol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-o
  • Polycyclic hetaryl groups have 2, 3, 4 or more than 4 fused rings.
  • the fused-on rings may be aromatic, saturated or partly unsaturated.
  • Examples of polycyclic hetaryl groups are quinolinyl, isoquinolinyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzoxazolyl, benzisoxazolyl, benzthiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, benzotriazinyl, benzoselenophenyl, thienothiophenyl, thienopyrimidyl, thiazolothiazolyl, dibenzopyrrolyl (carbazolyl), dibenzofuranyl, dibenzothioph
  • Substituted hetaryl groups may, depending on the number and size of their ring systems, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO 3 H, sulfonate, sulfamino, sulfamide, amidino, NE 13 E 14 where E 13 and E 14 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • Halogen substituents are preferably fluorine, chlorine or bromine.
  • the substituents are preferably selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxyl, carboxyl, halogen and cyano.
  • hetaryl also apply to the hetaryl moiety in hetaryloxy, hetarylthio, monohetarylamino and dihetarylamino.
  • acyl refers to alkanoyl or aroyl groups which generally have from 2 to 11, preferably from 2 to 8, carbon atoms, for example the acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl-, 2-ethylhexanoyl, 2-propylheptanoyl, pivaloyl, benzoyl or naphthoyl group.
  • the groups NE 1 E 2 , NE 3 E 4 , NE 5 E 6 , NE 7 E 8 , NE 9 E 10 , NE 11 E 12 and NE 13 E 14 are preferably N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-diisopropylamino, N,N-di-n-butylamino, N,N-di-t-butylamino, N,N-dicyclohexylamino or N,N-diphenylamino.
  • Fused ring systems can comprise alicyclic, aliphatic heterocyclic, aromatic and heteroaromatic rings and combinations thereof, hydroaromatic joined by fusion.
  • Fused ring systems comprise two, three or more (e.g. 4, 5, 6, 7 or 8) rings.
  • ortho-fusion i.e. each ring shares at least one edge or two atoms with each adjacent ring, and peri-fusion in which a carbon atom belongs to more than two rings.
  • Preferred fused ring systems are ortho-fused ring systems.
  • n denotes the number of naphthalene units which are bonded in the peri position and form the base skeleton of the inventive rylene compounds.
  • n denotes the particular naphthalene group of the rylene skeleton to which the radicals are bonded.
  • R n1 to R n4 radicals which are bonded to different naphthalene groups may each have identical or different definitions.
  • the compounds of the general formula I may be naphthalene diimides, perylenediimides, terrylenediimides or quaterrylenediimides of the following formulae:
  • the radicals R a and R b are independently of one another selected from hydrogen, linear C 1 -C 30 -alkyl, branched C 3 -C 30 -alkyl, perfluoro-C 1 -C 30 -alkyl, 1H,1H-perfluoro-C 2 -C 30 -alkyl, 1H,1H,2H,2H-perfluoro-C 3 -C 30 -alkyl, a radical of the formula G.1, a radical of the formula G.2 and a radical of the formula G.3 where
  • the radicals R a and R b are independently selected from radicals of the general formulae (G.1) (G.2) and (G.3).
  • R a and R b have the same meaning and are selected from radicals of the general formulae (G.1) (G.2) and (G.3).
  • the R m radicals are selected from C 1 -C 12 -alkyl or C 1 -C 12 -fluoroalkyl.
  • the R m radicals are selected from C 1 -C 4 -alkyl or C 1 -C 4 -fluoroalkyl.
  • the R n radicals are selected from C 1 -C 12 -alkyl.
  • R a and R b are each independently selected from radicals of the formula (G.2).
  • R a and R b are each independently selected from phenyl-(C 1 -C 30 )-alkyl groups, wherein the benzene ring of the phenylalkyl group bears 1, 2, 3, 4 or 5 substituents, independently selected from F, CI, Br, CN, C 1 -C 30 -alkyl and perfluoro-C 1 -C 30 -alkyl and the phenylalkyl group is attached to the imide nitrogen atom via the alkyl moiety of the phenylalkyl group.
  • R a and R b have the same meaning and are selected from phenyl-(C 1 -C 30 )-alkyl groups, wherein the benzene ring of the phenylalkyl group bears 1, 2, 3, 4 or 5 substituents, independently selected from F, CI, Br, CN, C 1 -C 30 -alkyl and perfluoro-C 1 -C 30 -alkyl.
  • R a and R b have the same meaning and are selected from phenyl-(C 1 -C 4 )-alkyl groups, wherein the benzene ring of the phenylalkyl group bears 1, 2, 3, 4 or 5 substituents, independently selected from F, CI, Br, CN, C 1 -C 30 -alkyl and perfluoro-C 1 -C 12 -alkyl.
  • R a and R b are each independently selected from radicals of the formula (G.1) mentioned in the following table 1.
  • R a and R b have the same meaning and are selected from radicals of the formula (G.1) mentioned in the following table 1.
  • R a and R b are each independently selected from radicals of the formula (G.2) mentioned in the following table 2.
  • R a and R b have the same meaning and are selected from radicals of the formula (G.2) mentioned in the following table 2.
  • R a and R b are each independently selected from linear C 1 -C 30 -alkyl radicals.
  • R a and R b have the same meaning and are selected from linear C 1 -C 30 -alkyl radicals.
  • Preferred linear alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.
  • R a and R b are each independently selected from branched C 3 -C 30 -alkyl radicals.
  • R a and R b have the same meaning and are selected from branched C 3 -C 30 -alkyl radicals.
  • radicals R a and R b are selected from radicals of the general formulae (111.1), (III.2) and (III.3) wherein
  • R e and R f are independently selected from C 1 - to C 20 -alkyl, especially C 1 - to C 12 -alkyl.
  • the sum of the carbon atoms of the radicals (111.1) is an integer from 3 to 55, more preferably from 4 to 40, in particular from 5 to 30.
  • Preferred radicals of the formula (111.1) are: 2-methylpropyl, 2-ethylbutyl, 2-methylbutyl, 2-propylpentyl, 2-ethylpentyl, 2-methylpentyl, 2-butylhexyl, 2-propylhexyl, 2-ethylhexyl, 2-methylhexyl, 2-pentylheptyl, 2-butylheptyl, 2-propylheptyl, 2-ethylheptyl, 2-methylheptyl, 2-hexyloctyl, 2-pentyloctyl, 2-butyloctyl, 2-propyloctyl, 2-ethyloctyl, 2-methyloctyl, 2-heptylnonyl, 2-hexylnonyl, 2-pentylnonyl, 2-butylnonyl, 2-propylnonyl, 2-ethylnonyl, 2-methylnony
  • Examples of preferred radicals of the formula (111.1) are 2 -ethylhexyl, 2-ethylheptyl, 2-ethyloctyl, 2-ethylnonyl and 2-ethyldecyl.
  • radicals R a and R b are each independently selected from radicals of the formula (III.2).
  • R a and R b have the same meaning and are selected from radicals of the formula (III.2).
  • Preferred radicals of the formula (III.2) are: 1-ethylpropyl, 1-methylpropyl, 1-propylbutyl, 1-ethylbutyl, 1-methylbutyl, 1-butylpentyl, 1-propylpentyl, 1-ethylpentyl, 1-methylpentyl, 1-pentylhexyl, 1-butylhexyl, 1-propylhexyl, 1-ethylhexyl, 1-methylhexyl, 1-hexylheptyl, 1-pentylheptyl, 1-butylheptyl, 1-propylheptyl, 1-ethylheptyl, 1-methylheptyl, 1-heptyloctyl, 1-hexyloctyl, 1-pentyloctyl, 1-butyloctyl, 1-propyloctyl, 1-ethyloctyl, 1-methyloctyl, 1-octylnon
  • radicals of the formula (III.2) are: 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 1-ethylpropyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylhexyl, 1-ethylheptyl, 1-ethyloctyl, 1-propylbutyl, 1-propylpentyl, 1-propylhexyl, 1-propylheptyl, 1-propyloctyl, 1-butylpentyl, 1-butylhexyl, 1-butylheptyl, 1-butyloctyl, 1-pentylhexyl, 1-pentylheptyl, 1-pentyloctyl, 1-hexylheptyl, 1-hexyloctyl, 1-heptyloctyl.
  • radicals R a and R b are each independently selected from radicals of the formula (III.3).
  • R a and R b have the same meaning and are selected from radicals of the formula (111.3).
  • a particularly preferred radical of the formula (III.3) is tert.-butyl.
  • At least one of the radicals R a and R b is selected from perfluoro-C 1 -C 30 -alkyl, 1H,1H-perfluoro-C 2 -C 30 -alkyl or 1H,1H,2H,2H-perfluoro-C 3 -C 30 -alkyl.
  • the radicals R a and R b are selected from perfluoro-C 1 -C 30 -alkyl, 1H,1H-perfluoro-C 2 -C 30 -alkyl or 1H,1H,2H,2H-perfluoro-C 3 -C 30 -alkyl.
  • At least one of the radicals R a and R b is selected from CF 3 , C 2 F 5 , n-C 3 F 7 , n-C 4 F 9 , n-C 5 F 11 ,n-C 6 F 13 , CF(CF 3 ) 2 , C(CF 3 ) 3 , CF 2 CF(CF 3 ) 2 , CF(CF 3 )(C 2 F 5 ), CH 2 -CF 3 , CH 2 -C 2 F 5 , CH 2 -(n-C 3 F 7 ), CH 2 -(n-C 4 F 9 ), CH 2 -(n-C 5 F 11 ), CH 2 -(n-C 6 F 13 ), CH 2 -CF(CF 3 ) 2 ,CH 2 -C(CF 3 ) 3 ,CH 2 -CF 2 CF(CF 3 ) 2 , CH 2 -CF(CF 3 )(C 2 F 5 ), CH 2 -CH 2 -CF 3 ), CH 2 -
  • WO 2012/090110 describes enantiomerically enriched mixtures that have unexpected electron-transport efficiency compared to the racemate or either of the enantiomers in optically pure form.
  • the substituents R a and R b are identical and selected from a branched C 4-40 alkyl group, a branched C 4-40 alkenyl group and a branched C 4-40 haloalkyl group, wherein the branched C 4-40 alkyl group, the branched C 4-40 alkenyl group, or the branched C 4-40 haloalkyl group are selected from: where R' is a C 1-20 alkyl or haloalkyl group; and R" is different from R' and selected from a C 1-20 alkyl group, a C 2-20 alkenyl group, and a C 1-20 haloalkyl group.
  • the asterisk * denotes a stereogenic center such that R a and R b have either an (R)- or an (S)-configuration.
  • the mixture is enantiomerically enriched, that is, the mixture includes an excess of either the (R,R)-stereoisomer (in which both R a and R b have the (R)-configuration) or the (S,S)-stereoisomer (in which both R a and R b have the (S)-configuration).
  • Preferred chiral substituents R a and R b are (1S)-1-methylbutyl, (1S)-1-methylpentyl, (1S)-1-methylhexyl, (1S)-1-methylheptyl, (1S)-1-methyloctyl, (1S)-1-ethylpropyl, (1S)-1-ethylbutyl, (1S)-1-ethylpentyl, (1S)-1-propylbutyl, (1S)-1-propylpentyl, (1S)-1-propylhexyl, (1R)-1-methylbutyl, (1R)-1-methylpentyl, (1R)-1-methylhexyl, (1R)-1-methylheptyl, (1R)-1-methyloctyl, (1R)-1-ethylpropyl, (1R)-1-ethylbutyl, (1R)-1-ethylpentyl, (1R)-1-propylbuty
  • a preferred class of compounds of the formula (I.a) are cyanated or halogenated rylene diimides, more preferably cyanated or halogenated perylene diimides, in particular N,N'-bis-substituted-(1,7 & 1,6)-di-cyano-perylene-3,4:9,10-bis(dicarboximide)s, N,N'-bis-substituted-(1,7 & 1,6)-di-fluoro-perylene-3,4:9,10-bis(dicarboximide)s, N,N'-bis-substituted-(1,7 & 1,6)-di-chloro-perylene-3,4:9,10-bis(dicarboximide)s and N,N'-bis-substituted-(1,7 & 1,6)-di-bromo-perylene-3,4:9,10-bis(dicarboximide)s.
  • Suitable cyanated or halogenated rylene diimides are described e.g. in U.S. Pat. Nos. 7,671,202 , 7,902,363 , and 7,569,693 , and U.S. Patent Application Publication No. 2010/0319778 .
  • the compounds of the formula (I.a) are selected from halogenated perylene bisimide derivatives described by R. Schmidt, J. H. Oh, Y.-S. Sun, M. Deppisch, A.-M. Krause, K. Radacki, H. Braunschweig, M. Könemann, P. Erk, Z. Bao and F. Würthner in J. Am. Chem. Soc. 2009, 131, 6215-6228 .
  • the compounds of the formula (I.a) are selected from perylenediimides as described in WO 2007/093643 and WO 2007/116001 .
  • component A) is selected from compounds of the general formula (I.a1) wherein
  • component A) comprises at least one compound of the formula (I.b) wherein
  • R 1b and R 2b are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl, unsubstituted branched C 3 -C 30 -alkyl, halogen substituted linear C 1 -C 30 -alkyl and halogen substituted branched C 3 -C 30 -alkyl.
  • R 1b and R 2b are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl, unsubstituted branched C 3 -C 30 -alkyl, linear C 1 -C 30 -fluoroalkyl and branched C 3 -C 30 -fluoroalkyl.
  • R 1b and R 2b are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl and unsubstituted branched C 3 -C 30 -alkyl.
  • R 1b and R 2b have the same meaning.
  • the compounds of the formula (I.b) are selected from compound of the formula (I.b1) wherein R 1b and R 2b are independently selected from linear C 7 -C 22 -alkyl and branched C 7 -C 22 -alkyl.
  • R 1b and R 2b have the same meaning.
  • R 1b and R 2b have the same meaning and are selected from linear C 7 -C 22 -alkyl.
  • component A) comprises at least one compound of the formula (I.c) wherein
  • Y 1c , Y 2c and Y 3c are all S.
  • R 1c and R 2c are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl, unsubstituted branched C 3 -C 30 -alkyl, halogen substituted linear C 1 -C 30 -alkyl and halogen substituted branched C 3 -C 30 -alkyl.
  • R 1c and R 2c are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl, unsubstituted branched C 3 -C 30 -alkyl, linear C 1 -C 30 -fluoroalkyl and branched C 3 -C 30 -fluoroalkyl.
  • R 1c and R 2c are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl and unsubstituted branched C 3 -C 30 -alkyl.
  • R 1c is hydrogen and R 2c is selected from linear C 1 -C 30 -alkyl and branched C 3 -C 30 -alkyl.
  • R 1c and R 2c are both selected from linear C 1 -C 30 -alkyl and branched C 3 -C 30 -alkyl.
  • the compounds of the formula (I.c) are selected from compound of the formula (I.c1) and (I.c2) wherein R 1c and R 2c are independently selected from linear C 7 -C 22 -alkyl and branched C 7 -C 22 -alkyl.
  • R 2c is selected from linear C 7 -C 22 -alkyl.
  • R 1c and R 2c have the same meaning.
  • R 1c and R 2c have the same meaning and are selected from linear C 7 -C 22 -alkyl.
  • R 1c and R 2c have the same meaning and are selected from n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
  • component A) comprises at least one compound of the formula (I.d) wherein
  • Y 1d , Y 2d , Y 3d and Y 4d are all S.
  • R 1d and R 2d are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl, unsubstituted branched C 3 -C 30 -alkyl, halogen substituted linear C 1 -C 30 -alkyl and halogen substituted branched C 3 -C 30 -alkyl.
  • R 1d and R 2d are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl, unsubstituted branched C 3 -C 30 -alkyl, linear C 1 -C 30 -fluoroalkyl and branched C 3 -C 30 -fluoroalkyl.
  • R 1d and R 2d are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl and unsubstituted branched C 3 -C 30 -alkyl.
  • R 1d is hydrogen and R 2d is selected from linear C 1 -C 30 -alkyl and branched C 3 -C 30 -alkyl.
  • R 1d and R 2d are both selected from linear C 1 -C 30 -alkyl and branched C 3 -C 30 -alkyl.
  • the compounds of the formula (I.d) are selected from compound of the formula (I.d1) and (I.d2) wherein R 1d and R 2d are independently selected from linear C 7 -C 22 -alkyl and branched C 7 -C 22 -alkyl.
  • R 2d selected from linear C 7 -C 22 -alkyl. More preferably, R 2d is selected from n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
  • R 1d and R 2d have the same meaning.
  • R 1d and R 2d have the same meaning and are selected from linear C 7 -C 22 -alkyl.
  • R 1d and R 2d have the same meaning and are selected from n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
  • component A) comprises at least one compound of the formula (I.e) wherein
  • Y 1e and Y 2e are both S or are both Se.
  • Y 1e and Y 2e are both S.
  • R 1e and R 2e are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl, unsubstituted branched C 3 -C 30 -alkyl, halogen substituted linear C 1 -C 30 -alkyl and halogen substituted branched C 3 -C 30 -alkyl.
  • R 1e and R 2e are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl, unsubstituted branched C 3 -C 30 -alkyl, linear C 1 -C 30 -fluoroalkyl and branched C 3 -C 30 -fluoroalkyl.
  • R 1e and R 2e are independently selected from hydrogen, unsubstituted linear C 1 -C 30 -alkyl and unsubstituted branched C 3 -C 30 -alkyl.
  • R 1e is hydrogen and R 2e is independently selected from unsubstituted linear C 1 -C 30 -alkyl, unsubstituted branched C 3 -C 30 -alkyl, halogen substituted linear C 1 -C 30 -alkyl and halogen substituted branched C 3 -C 30 -alkyl.
  • R 1e and R 2e are both selected from linear C 1 -C 30 -alkyl and branched C 3 -C 30 -alkyl.
  • the compounds of the formula (I.e) are selected from compound of the formula (I.e1) and (I.e2) wherein R 1e and R 2e are independently selected from unsubstituted linear C 7 -C 22 -alkyl and unsubstituted branched C 7 -C 22 -alkyl.
  • R 1e and R 2e have the same meaning.
  • R 1e and R 2e are selected from linear C 7 -C 22 -alkyl.
  • R 1e and R 2e have the same meaning and are selected from n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
  • composition according to the invention comprises as component B) at least one compound that is liquid at 20°C and 1013 mbar, selected from compounds of the formula (II) R c -X 1 -A-X 2 -R d wherein
  • the at least one organic semiconductor A) has a solubility in component B) at 20°C of at least 0.01 mg/ml, more preferably of at least 0.05 mg/ml.
  • the at least one organic semiconductor A) has a solubility in component B) at 20°C of less than 0.01 mg/ml
  • an additional cosolvent C selected from organic solvents and mixtures of organic solvents different from component B
  • the organic semiconductor A) has a solubility in the mixture of components B) and C) at 20°C of at least 0.01 mg/ml, preferably of at least 0.05 mg/ml.
  • an additional cosolvent C) if the at least one organic semiconductor A) has a sufficient solubility in component B) alone.
  • the additional cosolvent may be added to provide certain application properties, e.g. a good processability of the composition by a printing process.
  • the component B) is present in an amount of 0.1 to 99.9999999 wt.-%, preferably in an amount of 0.5 to 99.999999 wt.-%, more preferably in an amount of 1.0 to 99.99999 wt.-%, in particular in an amount of 10 to 99.99999 wt.-%, based on the total weight of the composition.
  • the component B) is present in an amount of 0.1 to 99.9999999 wt.-%, preferably in an amount of 0.5 to 99.999999 wt.-%, more preferably in an amount of 1.0 to 99.99999 wt.-%, in particular in an amount of 10 to 99.99999 wt.-%, based on the total weight of components A) and B).
  • component B) comprises at least one compound of the formula (II) with a Hansen solubility parameter (delta D) in the range of from 15 to 20, more preferably 16 to 19 mPa 1/2 .
  • component B) consists of at least one compound of the formula (II) with a Hansen solubility parameter (delta D) in the range of from 15 to 20, more preferably 16 to 19 mPa 1/2 .
  • component B) comprises at least one compound of the formula (II) with a Hansen solubility parameter (delta P) in the range of from 7 to 12, more preferably 8 to 11 mPa 1/2 .
  • component B) consists of at least one compound of the formula (II) with a Hansen solubility parameter (delta D) in the range of from 7 to 12, more preferably 8 to 11 mPa 1/2 .
  • component B) comprises at least one compound of the formula (II) with a Hansen solubility parameter (delta H) in the range of from 3.5 to 5.5, more preferably 4 to 5 mPa 1/2 .
  • component B) consists of at least one compound of the formula (II) with a Hansen solubility parameter (delta H) in the range of from 3.5 to 5.5, more preferably 4 to 5 mPa 1/2 .
  • component B) consists of at least one compound of the formula (II) with a boiling point at 1013,25 mbar of at least 100°C, more preferably of at least 150°C, in particular of at least 200°C.
  • component B) comprises at least one compound of the formula (II) with a boiling point at 1013,25 mbar in the range of 100 to 350°C, preferably 150 to 320°C.
  • component B) consists of at least one compound of the formula (II) with a boiling point at 1013,25 mbar in the range of 100 to 350°C, preferably 150 to 320°C.
  • the compound of the general formula (II) is selected from compounds of the formulae (11.1), (II.2), (II.3) and (II.4) wherein
  • the moieties R c and R d in the compounds of the formulae (II), (11.1), (11.2), (II.3), (II.4)and (II.5) are independently of each other an unbranched or branched C 7 -C 12 -alkyl moiety.
  • the moieties R c and R d in the compounds of the formulae (II), (11.1), (II.2), (11.3), (II.4) and (II.5) have the same meaning.
  • R c and R d are independently selected methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, isononyl, isodecyl, 2-propylheptyl, n-undecyl and isoundecyl.
  • the compound of the formula II.1 is selected from dimethylphthalate, diethylphthalate, di(n-propyl)phthalate, di(n-butyl)phthalate, diallylphthalate and mixtures thereof.
  • Suitable compounds of the general formula (II) and of the formulae (11.1), (II.2), (II.3) and (11.4) and methods for their production are known to a person skilled in the art.
  • plasticizers i.e. additives that are used to achieve desired processing properties or desired performance characteristics in many plastics.
  • Phthalic diesters (11.1) and terephthalic diesters (II.2) with alcohols of different chemical structure have in the past often been used as plasticizers because they have good compatibility with PVC and advantageous performance characteristics.
  • Short-chain phthalates e.g. dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), etc. are also used as gelling aids ("fast fuser").
  • Dialkylcyclohexane-1,2-dicarboxylic esters (11.3) can either be purchased or produced by processes known in the prior art.
  • the 1,2-cyclohexanedicarboxylic esters are generally obtained mostly via ring-hydrogenation of the corresponding phthalic esters.
  • the ring-hydrogenation can take place as mentioned above by the process described in WO 99/32427 .
  • a particularly suitable ring-hydrogenation process is also described by way of example in WO 2011/082991 A2 .
  • 1,2-Cyclohexanedicarboxylic esters can moreover be obtained via esterification of 1,2-cyclohexanedicarboxylic acid or of suitable derivatives thereof with the corresponding alcohols. The esterification can take place by conventional processes known to the person skilled in the art.
  • esters of 2,5-furandicarboxylic acid are another plasticizer class.
  • R. D. Sanderson et al. J. Appl. Pol. Sci., 1994, vol. 53, 1785-1793 ) describe the synthesis of esters of 2,5-furandicarboxylic acids and their use as plasticizers.
  • WO 2012/113608 describes C 5 -dialkyl esters of 2,5-furandicarboxylic acid
  • WO 2012/113609 describes C 7 -dialkyl esters of 2,5-furandicarboxylic acid
  • WO 2011/023490 describes Cg-dialkyl esters of 2,5-furandicarboxylic acid
  • WO 2011/023491 describes C 10 -dialkyl esters of 2,5-furandicarboxylic acid.
  • the compounds of the formula (11.2) are selected from dimethylterephthalate, diethylterephthalate, di(n-propyl)terephthalate, di(n-butyl)terephthalate, diallylterephthalate and mixtures thereof.
  • the compounds of the formula (11.3) are selected from dimethyl-1,2-cyclohexanedicarboxylate, diethyl-1,2-cyclohexanedicarboxylate, di(n-propyl)-1,2-cyclohexanedicarboxylate, di(n-butyl)-1,2-cyclohexanedicarboxylate, diallyl-1,2-cyclohexanedicarboxylate and mixtures thereof.
  • the compounds of the formula (11.4) are selected from dimethyl-2,5-furandicarboxylate, diethyl-2,5-furandicarboxylate, di(n-propyl)-2,5-furandicarboxylate, di(n-butyl)-2,5-furandicarboxylate, diallyl-2,5-furandicarboxylate and mixtures thereof.
  • the 2,5-furandicarboxylic acid or the di(C 1 -C 3 -alkyl) 2,5-furandicarboxylate obtained in step a) is subjected to esterification or transesterification with at least one alcohol R c -OH and, if R c and R d are different, also with at least one alcohol R d -OH, to give the compounds of the formula (II.5a), which are then hydrogenated to give compounds of the general formula (11.5) (step c1)).
  • Esterification catalysts that can be used are the catalysts conventionally used for this purpose, e.g. mineral acids, such as sulfuric acid and phosphoric acid; organic sulfonic acids, such as methanesulfonic acid and p-toluenesulfonic acid; amphoteric catalysts, in particular titanium compounds, tin(IV) compounds, or zirconium compounds, e.g. tetraalkoxytitanium compounds, e.g. tetrabutoxytitanium, and tin(IV) oxide.
  • the water produced during the reaction can be removed by conventional measures, e.g. by distillation.
  • WO 02/038531 describes a process for producing esters where a) a mixture consisting essentially of the acid component or an anhydride thereof and of the alcohol component is heated to boiling point in the presence of an esterification catalyst in a reaction zone, b) the vapors comprising alcohol and water are fractionated to give an alcohol-rich fraction and a water-rich fraction, c) the alcohol-rich fraction is returned to the reaction zone, and the water-rich fraction is discharged from the process.
  • Esterification catalysts used are the abovementioned catalysts. An effective amount of the esterification catalyst is used and is usually in the range from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight, based on the entirety of acid component (or anhydride) and alcohol component.
  • the esterification can generally take place at ambient pressure or at reduced or elevated pressure. It is preferable that the esterification is carried out at ambient pressure or reduced pressure.
  • the organic solvent used is inert under the reaction conditions.
  • these are by way of example aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, and aromatic and substituted aromatic hydrocarbons and ethers.
  • the solvent is one selected from pentane, hexane, heptane, ligroin, petrol ether, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dibutyl ether, THF, dioxane, and mixtures thereof.
  • esterification catalyst is one selected from organic acids or mineral acids
  • the esterification is usually carried out in the temperature range from 50 to 160°C.
  • esterification catalyst is one selected from amphoteric catalysts
  • the esterification is usually carried out in the temperature range from 100 to 250°C.
  • the esterification can take place in the absence of or in the presence of an inert gas.
  • the amount of transesterification catalyst used is from 0.001 to 10% by weight, preferably from 0.05 to 5% by weight.
  • the reaction mixture is preferably heated to the boiling point of the reaction mixture, the reaction temperature therefore being from 20°C to 200°C, depending on the reactants.
  • the transesterification can take place at ambient pressure or at reduced or elevated pressure. It is preferable that the transesterification is carried out at a pressure of from 0.001 to 200 bar, particularly from 0.01 to 5 bar.
  • the relatively low-boiling-point alcohol eliminated during the transesterification is preferably continuously removed by distillation in order to shift the equilibrium of the transesterification reaction.
  • the distillation column necessary for this purpose generally has direct connection to the transesterification reactor, and it is preferable that said column is a direct attachment thereto.
  • each of said reactors can have a distillation column, or the vaporized alcohol mixture can preferably be introduced into a distillation column from the final tanks of the transesterification reactor cascade by way of one or more collection lines.
  • the relatively high-boiling-point alcohol reclaimed in said distillation is preferably returned to the transesterification.
  • the transesterification can be carried out in the absence of, or in the presence of, an added organic solvent. It is preferable that the transesterification is carried out in the presence of an inert organic solvent. Suitable organic solvents are those mentioned above for the esterification. Among these are specifically toluene and THF.
  • EP-A 1266882 Use of a nickel/magnesium oxide on kieselguhr catalyst
  • WO 03/029181 Use of a nickel/zinc on silicon dioxide catalyst
  • WO 03/029168 Use of a palladium/ZnO on Al 2 O 3 catalyst and of a ruthenium/ZnO on ⁇ -Al 2 O 3 catalyst
  • WO 04/09526 Use of a ruthenium on titanium dioxide catalyst.
  • Other suitable catalysts are likewise Raney catalysts, preferably Raney nickel.
  • ZrO 2 zirconium dioxide
  • sulfated zirconium dioxide tungsten carbide
  • TiO 2 titanium dioxide
  • sulfated carbon activated charcoal, aluminum phosphate, aluminosilicates, or phosphated aluminum oxide, or else a combination thereof.
  • the hydrogenation can take place by analogy with the known hydrogenation processes for hydrogenating organic compounds which have hydrogenatable groups.
  • the organic compound in the form of liquid phase or gas phase preferably in the form of liquid phase, is brought into contact with the catalyst in the presence of hydrogen.
  • the liquid phase can by way of example be passed over a fluidized bed of catalyst (fluidized bed method) or can be passed over a fixed bed of catalyst (fixed bed method).
  • an organic solvent that is inert under the hydrogenation conditions.
  • Suitable solvents are those previously defined for the esterification.
  • an ether is used, for example THF, or a dialkylene glycol, or a mono- or diether thereof, for example glyme.
  • the amount of hydrogen used for the hydrogenation is generally from 1 to 15 times the stochiometric amount of hydrogen theoretically needed for the complete hydrogenation of the furan ring.
  • composition according to the invention comprises a cosolvent C) selected from organic solvents different from component B) and mixtures of organic solvents different from component B).
  • the component B) is present in an amount of 0.1 to 100 wt.-%, preferably in an amount of 1 to 100 wt.-%, more preferably in an amount of 10 to 100 wt.-%, in particular in an amount of 50 to 100 wt.-%, based on the total weight of components B) and C).
  • the component C) is present in an amount of 0 to 99.9 wt.-%, preferably in an amount of 0 to 99 wt.-%, more preferably in an amount of 0 to 90 wt.-%, in particular in an amount of 0 to 50 wt.-%, based on the total weight of components B) and C).
  • the amount is preferably 0.1 to 99.9 wt.-%, more preferably 1 to 99 wt.-%, in particular 2 to 90 wt.-%, especially 3 to 50 wt.-%, based on the total weight of components B) and C).
  • the cosolvent C) is selected from
  • Preferred aromatic ethers are anisole (methylphenylether) ethoxybenzene (phenetol), propoxybenzene, isopropoxybenzene, butoxybenzene, 1-methoxynaphthalin, 2-methoxynaphthalin, 2-methylanisole, 3-methylanisole, 4-methylanisole, 2-ethylanisole, 3-ethylanisole, 4-ethylanisole, 2,3-dimethylanisole, 2,4-dimethylanisole, 2,5-dimethylanisole, 2,6-dimethylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, 1,2-dimethoxybenzene (veratrol), 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 1-ethoxy-4-methoxybenzene, 1-ethoxy-3-methoxybenzene, 1-ethoxy-2-methoxybenzene, 1,2-diethoxybenzene, 1,3-diethoxybenzene, 1,
  • ketones are acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl n-amyl ketone, diisobutyl ketone, cyclohexanone, pentane-2,4-dione (acetylacetone), acetophenone, 2-acetyltoluene, 3-acetyltoluene, 4-acetyltoluene, propiophenone, butyrophenone, valerophenone, hexanophenone and mixtures thereof.
  • Preferred cosolvent C) are acetylacetone, acetophenone and mixtures thereof.
  • Preferred esters are ethyl acetate, methyl acetate, ethyl acetoacetate, propyl acetate, isopropyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, isobutyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl butyrate, ethyl lactate, diethyl carbonate, ethylene carbonate, propylene carbonate, triacetin, phenyl formate, phenyl acetate, o-cresol acetate, p-cresol acetate, m-Cresol acetate, 2-methoxyphenyl acetate, 3-methoxyphenyl acetate, and 4-methoxyphenyl acetate, benzyl benzoate, bis(2-ethylhexyl) adipate, methyl
  • Preferred halogenated aromatic compounds are selected from chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,4-trichlorobenzene, 4-chlorotoluene, 3-chlorobenzene, 2-chlorotoluene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1-chloronaphthalene, 2-chloronaphthalene, 1-fluoronaphthalene, 2-fluoronaphthalene, 2-chloroanisole, 3-chloroanisole, 4-chloroanisole, 4-fluoroanisole, 3-fluoroanisole, 2-fluoroanisole,and mixtures thereof.
  • thiophenols examples include thiophenol, 2-thiocresol, 3-thiocresol, 4-thiocresol, 2-ethyl thiophenol, 3-ethyl thiophenol, 4-ethyl thiophenol, 2,6-dimethylthiophenol, 2,5-dimethylthiophenol, 2,4-dimethylthiophenol, 2,3-dimethylthiophenol, and 2-isopropylthiophenol.
  • alkylthio-substituted benzenes examples include thioanisole, (ethylthio)benzene, 2-methylthioanisole, 3-methyl thioanisole, 4-methyl thioanisole, 4-methoxy thioanisole, 3-methoxy thioanisole, 2-methoxy thioanisole.
  • Suitable aromatic compounds comprising a phenyl group fused to a 5-, 6-, or 7-membered cycloheteroalkyl group include indoline and substituted indolines, such as 7-methylindoline, 5-methylindoline, and 6-methylindoline; 1,2,3,4-tetrahydroquinoline; 6-methyl-3,4-dihydro-2H-1-benzopyran; benzodioxole and substituted benzodioxoles, such as 1,3-benzodioxole, 2-methyl-1,3-benzodioxole, 2-ethyl-1,3-benzodioxole, 5-hydroxy-1,3-benzodioxole, 5-methyl-1,3-benzodioxole, 5-methoxy-1,3-benzodioxole, 5-methyl-1,3-benzodioxole, 5-ethyl-1,3-benzodioxole
  • Suitable 5-membered heteroaryl compounds and benzo-fused 5-membered heteroaryl compounds are thiophene, 2-methylthiophene, 3-methylthiophene, furan, 3-methylfuran, 2-methylfuran, pyrrole, N-methylpyrrole, N-ethylpyrrole, 1,2-dimethyl-1H-pyrrole, 1,3-dimethyl-1H-pyrrole, 2-methoxyfuran, 3-methoxyfuran, 3-methoxythiophene, 2-methoxythiophene, 2-methylthiofuran, 3-methylthiofuran, 3-methylthiothiophene, 2-methylthiothiophene, 2-N,N-dimethylamino-thiophene, 3-methoxy-1-methyl-1H-pyrrole, 2-methoxy-1-methyl-1H-pyrrole, benzofuran, 6-methylbenzofuran, benzothiophene, and 6-methylbenzothiophene.
  • Suitable aromatic aldehydes are benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 4-ethylbenzaldehyde, 3-ethylbenzaldehyde, 2-ethylbenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 4-fluorobenzaldehyde, 3-fluorobenzaldehyde, 2-fluorobenzaldehyde, 2-bromobenzaldehyde, 3-bromobenzaldehyde, and 4-bromobenzaldehyde.
  • Suitable trifluoromethyl-substituted benzene compounds are benzotrifluoride, 2-methylbenzotrifluoride, 3-methylbenzotrifluoride, 4-methylbenzotrifluoride, 4-chlorobenzotrifluoride, 3-chlorobenzotrifluoride, 2-chlorobenzotrifluoride, 2-fluorobenzotrifluoride, 3-fluorobenzotrifluoride, 4-fluorobenzotrifluoride, 4-bromobenzotrifluoride, 3-bromobenzotrifluoride, 2-bromobenzotrifluoride, methyl 2-trifluoromethylbenzoate, methyl 3-trifluoromethylbenzoate, methyl 4-trifluoromethylbenzoate, ethyl 2-trifluoromethylbenzoate, ethyl 3-trifluoromethylbenzoate, ethyl 4-trifluoromethylbenzoate and mixtures thereof.
  • Suitable cyano-substituted or isocyano-substituted benzene compounds are benzonitrile, 2-methylbenzenecarbonitrile, 3-methylbenzenecarbonitrile, 4-methylbenzenecarbonitrile, 4-chlorobenzonitrile, 3-chlorobenzonitrile, 2-chlorobenzonitrile, 2-fluorobenzonitrile, 3-fluorobenzonitrile, 4-fluorobenzonitrile, phenylisocyanide, 2-tolylisocyanide, 3-tolylisocyanide, 4-tolylisocyanide and mixtures thereof.
  • Suitable nitro-substituted benzene compounds are nitrobenzene, 2-nitrotoluene, 3-nitrotoluene, 4-nitrotoluene, 1-chloro-4-nitrobenzene, 1-chloro-3-nitrobenzene, 1-chloro-2-nitrobenzene, 1-fluoro-2-nitrobenzene, 1-fluoro-3-nitrobenzene, 1-fluoro-4-nitrobenzene and mixtures thereof.
  • Suitable phenyl sulfones are methyl phenyl sulfone, ethyl phenyl sulfone, (propane-1-sulfonyl)benzene, 1-methanesulfonyl-2-methyl-benzene, 1-methanesulfonyl-3-methylbenzene, and 1-methanesulfonyl-4-methyl-benzene.
  • Suitable 6-membered heteroaryl compounds or benzofused 6-membered heteroaryl compounds are pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 4-fluoropyridine, 3-fluoropyridine, 2-fluoropyridine, 2-bromo-pyridine, 3-bromo-pyridine, 4-bromo-pyridine, 4-(trifluoromethyl)pyridine, 3-(trifluoromethyl)pyridine, 2-(trifluoromethyl)pyridine, 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine, 4-nitropyridine, 3-nitropyridine, 2-nitropyridine, 2-picolinic acid methyl ester, 3-picolinic acid methyl ester, and 4-picolinic acid methyl ester; pyrazine and substituted pyrazines, such as methylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3-
  • Suitable aprotic polar solvents are acetonitrile, formamide, dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide (DMSO), N-methylpyrrolidone, (CH 3 ) 2 SO, dimethyl sulfone, sulfolane, cyclic ureas, such as 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), imidazolidin-2-one and mixtures thereof.
  • the composition according to the invention contains the viscosity-modifying additive in an amount of 0.1 to 30 wt.-%, preferably 0.2 to 20 wt.-%, based on the total weight of component B) and the viscosity-modifying additive.
  • a further object of the invention is a process for the preparation of an electronic device, optical device or optoelectronic device, comprising:
  • step (b) the application of the composition provided in step (a) to at least a portion of the surface of the substrate is performed by printing.
  • substrates may be used in the method of the present invention.
  • the substrates may be made of virtually any materials which are stable under the process conditions of the method of the invention.
  • the substrate may include organic and inorganic materials or composite materials.
  • Suitable substrates are in principle all materials known for this purpose. Suitable substrates comprise, for example, oxidic materials, metals, semiconductors, metal alloys, semiconductor alloys, polymers, inorganic solids, paper and combinations thereof.
  • Suitable substrates are preferably selected from SiO 2 , inorganic glasses, quartz, ceramics, undoped or doped inorganic semiconductors, metals of groups 8, 9, 10 or 11 of the Periodic Table and metal alloys thereof, polymeric materials, filled polymeric materials and combinations thereof.
  • At least the surface of the substrate comprises or consists of at least one dielectric.
  • Suitable dielectrics are selected from inorganic dielectric materials, polymeric dielectric materials and combinations thereof.
  • Suitable inorganic dielectric materials are SiO 2 , Al 2 O 3 , ZrO 2 , HfO 2 , TaO5, WO 3 SiO 3 N 4 , RbBr, LiF, BaTiO 3 , PbTiO 3 , and mixtures thereof.
  • Suitable polymeric dielectric materials are polystyrene, poly- ⁇ -methylstyrene, polyolefins (such as polypropylene, polyethylene, polyisobutene), polyvinylcarbazole, fluorinated polymers (e.g.
  • Cytop, CYMM cyanopullulans
  • polyvinylphenol poly-p-xylene
  • polyvinyl chloride poly(methyl methacrylate)/trimethylolpropane triacrylate copolymers etc.
  • Specific dielectrics are "self-assembled nanodielectrics", i.e. polymers which are obtained from monomers comprising SiCI functionalities, for example Cl 3 SiOSiCl 3 , Cl 3 Si-(CH 2 ) 6 -SiCl 3 , Cl 3 Si-(CH 2 ) 12 -SiCl 3 , and/or which are crosslinked by atmospheric moisture or by addition of water diluted with solvents (see, for example, Facchetti Adv. Mat.
  • hydroxyl-containing polymers such as polyvinylphenol or polyvinyl alcohol or copolymers of vinylphenol and styrene to serve as crosslinking components. It is also possible for at least one further polymer to be present during the crosslinking operation, for example polystyrene, which is then also crosslinked (see Facchetti, US patent application 2006/0202195 ).
  • SAM self-assembled monolayer
  • Suitable compounds for the surface modification are:
  • the compounds for the surface modification are preferably selected from alkyltrichlorosilanes, alkyltrialkoxysilanes, hexaalkyldisilazanes, C 8 -C 30 -alkylthiols, mercaptocarboxylic acids, mercaptosulfonic acids and mixtures thereof.
  • the compounds for the surface modification are selected from n-octadecyltrichlorosilane (OTS), n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, hexamethyldisilazane (HMDS), 4-ethoxyphenylphosphonic acid, hexadecanethiol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid and 3-mercapto-1-propanesulfonic acid, the alkali metal and ammonium salts of mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid and 3-mercapto-1-propanesulfonic acid and mixtures thereof.
  • OTS n-octadecyltrichlorosilane
  • HMDS hexamethyldisilazane
  • 4-ethoxyphenylphosphonic acid
  • An aspect of the present teaching relates to the fabrication of an organic field-effect transistor that incorporates a semiconductor component prepared from a composition according to the invention.
  • An OFETs generally comprises a substrate having at least one gate structure including a gate electrode and a gate dielectric, a source electrode and a drain electrode and a semiconductor material that is in contact with the source and drain electrode and the gate dielectric.
  • a specific embodiment is a substrate with a pattern (topography) of organic field-effect transistors, each transistor comprising
  • a further specific embodiment is a substrate having a pattern of organic field-effect transistors, each transistor forming an integrated circuit or being part of an integrated circuit and at least some of the transistors are prepared by deposition of an organic semiconductor from a composition according to the invention.
  • Suitable substrates are those mentioned above.
  • a typical substrate for semiconductor units comprises a matrix (for example a silicon, quartz or polymer matrix) and, optionally, a dielectric top layer.
  • Suitable dielectrics are those mentioned above, wherein SiO 2 is especially preferred.
  • the substrate may additionally have electrodes, such as gate, drain and source electrodes of OFETs, which are normally localized on the substrate (for example deposited onto or embedded into a nonconductive layer on the dielectric).
  • the substrate may additionally comprise conductive gate electrodes of the OFETs, which are typically arranged below the dielectric top layer (i.e. the gate dielectric).
  • drain and source electrodes are present at least partly on the organic semiconductor material.
  • the substrate may comprise further components as used customarily in semiconductor materials or ICs, such as insulators, resistors, capacitors, conductor tracks, etc.
  • the electrodes may be applied by customary processes, such as evaporation or sputtering, lithographic processes or another structuring process, such as printing techniques.
  • the resulting semiconductor layers generally have a thickness which is sufficient for forming a semiconductor channel which is in contact with the source/drain electrodes.
  • the semiconductor component is preferably deposited on the substrate in a thickness of from 0.5 to 1000 nm, more preferably from 1.5 to 250 nm.
  • the surface of the substrate, before the deposition of at least one compound of the general formula A) is subjected to a modification as mentioned above.
  • composition according to the invention for example top contact, top gate, bottom contact, bottom gate, or else a vertical construction, for example a VOFET (vertical organic field-effect transistor), as described, for example, in US 2004/0046182 .
  • VOFET vertical organic field-effect transistor
  • Preferred semiconductor architectures are the following:
  • the layer thicknesses are, for example, from 0.5 nm to 5 ⁇ m in semiconductors, from 3 nm to 10 ⁇ m in the dielectric; the electrodes may, for example, be from 20 nm to 10 ⁇ m.
  • the OFETs may also be combined to form other components, such as ring oscillators or inverters.
  • a further aspect of the invention is the provision of electronic components which comprise a plurality of semiconductor components, which may be n- and/or p-semiconductors.
  • semiconductor components which may be n- and/or p-semiconductors.
  • FETs field-effect transistors
  • BJTs bipolar junction transistors
  • tunnel diodes converters
  • light-emitting components biological and chemical detectors or sensors
  • temperature-dependent detectors temperature-dependent detectors
  • photodetectors such as polarization-sensitive photodetectors, gates, AND, NAND, NOT, OR, TOR and NOR gates, registers, switches, timer units, static or dynamic stores and other dynamic or sequential, logical or other digital components including programmable switches.
  • composition according to the invention is also particularly suitable for use in organic photovoltaics (OPVs).
  • OOVs organic photovoltaics
  • An aspect of the present teaching relates to the fabrication of organic solar cells, e.g. solar cells which are characterized by diffusion of excited states (exciton diffusion). In this case, one or both of the semiconductor materials utilized is notable for a diffusion of excited states (exciton mobility).
  • Organic solar cells generally have a layer structure and generally comprise at least the following layers: anode, photoactive layer and cathode. These layers are generally applied to a substrate suitable for this purpose. The structure of organic solar cells is described, for example, in US 2005/0098726 and US 2005/0224905 .
  • a representative organic solar cell comprises a substrate with at least one cathode and at least one anode and at least one photoactive region comprising a semiconductor material.
  • a photoactive region may comprise two layers, each of which has a homogeneous composition and forms a flat donor-acceptor heterojunction.
  • a photoactive region may also comprise a mixed layer and form a donor-acceptor heterojunction in the form of a donor-acceptor bulk heterojunction.
  • Suitable substrates for organic solar cells are those mentioned above, for example, oxidic materials, polymers and combinations thereof.
  • Preferred oxidic materials are selected from glass, ceramic, SiO 2 , quartz, etc.
  • Preferred polymers are selected from polyethylene terephthalates, polyolefins (such as polyethylene and polypropylene), polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth)acrylates, polystyrenes, polyvinyl chlorides and mixtures and composites.
  • Suitable electrodes are in principle metals, semiconductors, metal alloys, semiconductor alloys, nanowire thereof and combinations thereof.
  • Preferred metals are those of groups 2, 8, 9, 10, 11 or 13 of the periodic table, e.g. Pt, Au, Ag, Cu, Al, In, Mg or Ca.
  • Preferred semiconductors are, for example, doped Si, doped Ge, indium tin oxide (ITO), fluorinated tin oxide (FTO), gallium indium tin oxide (GITO), zinc indium tin oxide (ZITO), poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT-PSS), etc.
  • Preferred metal alloys are, for example, alloys based on Pt, Au, Ag, Cu, etc. A specific embodiment is Mg/Ag alloys.
  • the material used for the electrode facing the light is preferably a material at least partly transparent to the incident light.
  • This preferably includes electrodes which have glass and/or a transparent polymer as a carrier material.
  • Transparent polymers suitable as carriers are those mentioned above, such as polyethylene terephthalate.
  • the electrical contact connection is generally effected by means of metal layers and/or transparent conductive oxides (TCOs). These preferably include ITO, doped ITO, FTO (fluorine doped tin oxide), AZO (aluminum doped tin oxide), ZnO, TiO 2 , Ag, Au, Pt or graphene or multi layer graphene or carbon nanotubes.
  • ITO for contact connection.
  • a conductive polymer for example a poly-3,4-alkylenedioxythiophene, e.g. poly-3,4-ethyleneoxythiophene poly(styrenesulfonate) (PEDOT).
  • PEDOT poly-3,4-alkylenedioxythiophene
  • PEDOT poly-3,4-ethyleneoxythiophene poly(styrenesulfonate)
  • the electrode facing the light is configured such that it is sufficiently thin to bring about only minimal light absorption but thick enough to enable good charge transport of the extracted charge carriers.
  • the thickness of the electrode layer (without carrier material) is preferably within a range from 20 to 200 nm.
  • the material used for the electrode facing away from the light is a material which at least partly reflects the incident light.
  • the thickness of the electrode layer is preferably within a range from 20 to 300 nm.
  • the solar cells preferably comprise at least one photoactive donor-acceptor heterojunction.
  • Optical excitation of an organic material generates excitons.
  • the electron-hole pair has to be separated, typically at a donor-acceptor interface between two unlike contact materials.
  • the donor material forms a heterojunction with an acceptor material.
  • quenching either radiatively by the emission of light of a lower energy than the incident light or nonradiatively by generation of heat. Both processes are undesired.
  • At least one compound of the general formula (I) is used as an n-semiconductor (electron conductor, acceptor) it is employed as the ETM (electron transport material) of the solar cell. It can then be combined with an appropriate p-semiconductor (electron donor material) that is employed as the HTM (hole transport material) of the solar cell.
  • Hole-conducting materials preferably comprise at least one material with high ionization energy. The materials may be organic or inorganic materials.
  • Suitable HTMs are, for example, N,N'-Bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-dimethylfluoren, N,N'-Bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-diphenylfluoren, N,N'-Bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-diphenylfluoren, N,N'-Bis(naphthalen-1-yl)-N,N'-bis(phenyl)-2,2-dimethylbenzidin, N,N'-Bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-spirobifluoren, 2,2',7,7'-Tetrakis(N,N-diphenylamino)-9,9'-spirobifluoren, N,N'-Bis(n
  • PEDOT poly (3,4-ethylene-dioxythiophene), polyvinylcarbazole (PVK), poly(N,N'-bis (4-butylphenyl)-N,N'-bis(phenyl) benzidine (PTPD), polyaniline (PANI) and poly (3-hexylthiophene (P3HT).
  • PEDOT poly (3,4-ethylene-dioxythiophene)
  • PVK polyvinylcarbazole
  • PTPD poly(N,N'-bis (4-butylphenyl)-N,N'-bis(phenyl) benzidine
  • PANI polyaniline
  • P3HT poly (3-hexylthiophene
  • the heterojunction has a flat configuration (see: Two layer organic photovoltaic cell, C. W. Tang, Appl. Phys. Lett., 48 (2), 183-185 (1986 ) or N. Karl, A. Bauer, J. Holzäpfel, J. Tanner, M. Möbus, F. Stölzle, Mol. Cryst. Liq. Cryst., 252, 243-258 (1994 ).).
  • composition according to the invention can also be used for the fabrication of the photoactive material in tandem cells.
  • Suitable tandem cells are described, for example, by P. Peumans, A. Yakimov, S. R. Forrest in J. Appl. Phys., 93 (7), 3693-3723 (2003 ) (see also US 4,461,922 , US 6,198,091 and US 6,198,092 ) and are described in detail hereinafter.
  • composition according to the invention can also be used for the fabrication of the photoactive material in tandem cells which are constructed from two or more than two stacked MiM, pin, Mip or Min structures (see DE 103 13 232.5 and J. Drechsel et al., Thin Solid Films, 451452, 515-517 (2004 )).
  • the layer thickness of the M, n, i and p layers is typically within a range from 10 to 1000 nm, more preferably from 10 to 400 nm.
  • the other layers which form the solar cell can be produced by customary processes known to those skilled in the art. These include vapor deposition under reduced pressure or in an inert gas atmosphere, laser - ablation or solution or dispersion processing methods such as spincoating, knifecoating, casting methods, spray application, dipcoating or printing (e.g. inkjet, flexographic, offset, gravure; intaglio, nanoimprinting). In a specific embodiment, the entire solar cell is produced by solution processing.
  • the solar cells are present as an individual cell with flat heterojunction and normal structure.
  • the cell has the following structure:
  • the essentially transparent conductive layer (11) (anode) comprises a carrier, such as glass or a polymer (e.g. polyethylene terephthalate) and a conductive material, as described above. Examples include ITO, doped ITO, FTO, ZnO, AZO, etc.
  • the anode material can be subjected to a surface treatment, for example with UV light, ozone, oxygen plasma, Br 2 , etc.
  • the layer (11) should be sufficiently thin to enable maximum light absorption, but also sufficiently thick to ensure good charge transport.
  • the layer thickness of the transparent conductive layer (11) is preferably within a range from 20 to 200 nm.
  • This layer comprises at least one hole-conducting material (hole transport material, HTM).
  • Hole-conducting materials (HTM) suitable for forming layers with hole-conducting properties (HTL) preferably comprise at least one material with high ionization energy.
  • the ionization energy is preferably at least 5.0 eV, more preferably at least 5.5 eV.
  • the materials may be organic or inorganic materials.
  • Organic materials suitable for use in a layer with hole-conducting properties are preferably selected from poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT-PSS), Ir-DPBIC (tris-N,N'-diphenylbenzimidazol-2-ylideneiridium(III)), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine (a-NPD), 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-MeOTAD), etc.
  • PEDOT-PSS poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
  • Ir-DPBIC tris-N,N'-diphenylbenzimidazol-2-
  • the organic materials may, if desired, be doped with a p-dopant which has a LUMO within the same range as or lower than the HOMO of the hole-conducting material.
  • Suitable dopants are, for example, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ), WO 3 , MoO 3 , etc.
  • Inorganic materials suitable for use in a layer with hole-conducting properties are preferably selected from WO 3 , MoO 3 , etc.
  • the thickness of the layers with hole-conducting properties is preferably within a range from 5 to 200 nm, more preferably 10 to 100 nm.
  • Layer (13) comprises at least one donor material.
  • the thickness of the layer should be sufficient to absorb a maximum amount of light, but thin enough to enable effective dissipation of the charge.
  • the thickness of the layer (13) is preferably within a range from 5 nm to 1 ⁇ m, more preferably from 5 to 100 nm.
  • Layer (14) comprises at least acceptor material.
  • the thickness of the layer should be sufficient to absorb a maximum amount of light, but thin enough to enable effective dissipation of the charge.
  • the thickness of the layer (14) is preferably within a range from 5 nm to 1 ⁇ m, more preferably from 5 to 80 nm.
  • Suitable donor and acceptor materials are in principle organic semiconductors, wherein at least one is a semiconductor A) deposited fro a composition according to the invention.
  • Solar cells with normal structure optionally comprise an exciton-blocking and/or electron-conducting layer (15) (EBL/ETL).
  • Suitable materials for exciton-blocking layers generally have a greater band gap than the materials of layer (13) and/or (14). They are firstly capable of reflecting excitons and secondly enable good electron transport through the layer.
  • the materials for the layer (15) may comprise organic or inorganic materials.
  • Layer 16 is the cathode and preferably comprises at least one compound with low work function, more preferably a metal, such as Ag, Al, Mg, Ca, etc.
  • the thickness of the layer (16) is preferably within a range from about 10 nm to 10 ⁇ m, e.g. 10 nm to 60 nm.
  • the inventive solar cells are present as an individual cell with a flat heterojunction and inverse structure.
  • the cell has the following structure:
  • the inventive solar cell is a tandem cell.
  • a tandem cell consists of two or more than two (e.g. 3, 4, 5, etc.) subcells.
  • a single subcell, some of the subcells or all subcells may have photoactive donor-acceptor heterojunctions.
  • Each donor-acceptor heterojunction may be in the form of a flat heterojunction or in the form of a bulk heterojunction.
  • the photoactive layer of at least one subcell is prepared from a composition according to the invention.
  • the subcells which form the tandem cell may be connected in parallel or in series.
  • the subcells which form the tandem cell are preferably connected in series.
  • the individual subcells have the same polarity, i.e. generally either only cells with normal structure or only cells with inverse structure are combined with one another.
  • Subcell refers here to a cell as defined above without cathode and anode.
  • the subcells may, for example, either all have polymorph 2 in the photoactive layer or have other combinations of semiconductor materials, for example C60 with zinc phthalocyanine, C60 with oligothiophene (such as DCV5T).
  • individual subcells may also be configured as dye-sensitized solar cells or polymer cells.
  • Acenes such as anthracene, tetracene, pentacene and substituted acenes.
  • Substituted acenes comprise at least one substituent selected from electron-donating substituents (e.g. alkyl, alkoxy, ester, carboxylate or thioalkoxy), electron-withdrawing substituents (e.g. halogen, nitro or cyano) and combinations thereof.
  • Phthalocyanines such as hexadecachlorophthalocyanines and hexadecafluorophthalocyanines, metal-free phthalocyanine and phthalocyanine comprising divalent metals, especially those of titanyloxy, vanadyloxy, iron, copper, zinc, especially copper phthalocyanine, zinc phthalocyanine and metal-free phthalocyanine, copper hexadecachlorophthalocyanine, zinc hexadecachlorophthalocyanine, metal-free hexadecachlorophthalocyanine, copper hexadecafluorophthalocyanine, hexadecafluorophthalocyanine or metal-free hexadecafluorophthalocyanine.
  • divalent metals especially those of titanyloxy, vanadyloxy, iron, copper, zinc, especially copper phthalocyanine, zinc phthalocyanine and metal-free phthalocyanine, copper hexadecachlor
  • Porphyrins for example 5,10,15,20-tetra(3-pyridyl)porphyrin (TpyP).
  • Preferred thiophenes, oligothiophenes and substituted derivatives thereof are poly-3-hexylthiophene (P3HT) or compounds of the ⁇ ⁇ '-bis(2,2-dicyanovinyl)quin-quethiophene (DCV5T) type, poly(3-(4-octylphenyl)-2,2'-bithiophene) (PTOPT), poly(3-(4'-(1",4",7"-trioxaoctyl)phenyl)thiophene) (PEOPT), poly(3-(2'-methoxy-5'-octylphenyl)thiophenes) (POMeOPTs), poly(3-octylthiophene) (P3OT), pyridine-containing polymers such as poly(pyridopyrazine vinylene), poly(pyridopyrazine vinylene) modified with alkyl groups e.g
  • Paraphenylenevinylene and paraphenylenevinylene-comprising oligomers and polymers for example polyparaphenylenevinylene (PPV), MEH-PPV (poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene)), MDMO-PPV (poly(2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene)), cyano-paraphenylenevinylene (CN-PPV), CN-PPV modified with alkoxy groups.
  • PV polyparaphenylenevinylene
  • MEH-PPV poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene)
  • MDMO-PPV poly(2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene)
  • Polyfluorenes and alternating polyfluorene copolymers for example with 4,7-dithien-2'-yl-2,1,3-benzothiadiazoles, and also poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F 8 BT), poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylenediamine) (PFB).
  • Polycarbazoles i.e. carbazole-comprising oligomers and polymers, such as (2,7) and (3,6).
  • Polyanilines i.e. aniline-comprising oligomers and polymers.
  • Triarylamines polytriarylamines, polycyclopentadienes, polypyrroles, polyfuran, polysilols, polyphospholes, N,N'-Bis-(3-methylphenyl)-N,N'-bis-(phenyl)-benzidine (TPD), 4,4'-bis(carbazol-9-yl) biphenyl (CBP), 2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene (spiro-MeOTAD).
  • TPD N,N'-Bis-(3-methylphenyl)-N,N'-bis-(phenyl)-benzidine
  • CBP 4,4'-bis(carbazol-9-yl) biphenyl
  • spiro-MeOTAD 2,2',7,7'-tetrakis-(N,N-di-p-methoxypheny
  • PCBM [6,6]-phenyl-C 61 -butyric acid methyl ester
  • p-n-Mixed materials i.e. donor and acceptor in one material, polymer, block copolymers, polymers with C60s, C60 azo dyes, trimeric mixed material which comprises compounds of the carotenoid type, porphyrin type and quinoid liquid-crystalline compounds as donor/acceptor systems, as described by Kelly in S. Adv. Mater. 2006, 18, 1754 .
  • An aspect of the present teaching relates to the fabrication of an electroluminescent (EL) arrangement comprising an upper electrode, a lower electrode, wherein at least one of said electrodes is transparent, an electroluminescent layer and optionally an auxiliary layer, wherein the electroluminescent arrangement comprises a semiconductor component prepared fro a composition according to the invention.
  • An EL arrangement is characterized by the fact that it emits light when an electrical voltage is applied with flow of current. Such arrangements have been known for a long time in industry and technology as light-emitting diodes (LEDs). Light is emitted on account of the fact that positive charges (holes) and negative charges (electrons) combine with the emission of light.
  • This structure represents the most general case and can be simplified by omitting individual layers, so that one layer performs several tasks.
  • an EL arrangement consists of two electrodes between which an organic layer is arranged, which fulfills all functions, including emission of light.
  • the structure of organic light-emitting diodes and processes for their production are known in principle to those skilled in the art, for example from WO 2005/019373 .
  • Suitable materials for the individual layers of OLEDs are disclosed, for example, in WO 00/70655 . Reference is made here to the disclosure of these documents.
  • OLEDs according to the invention can be produced by methods known to those skilled in the art.
  • the OLED can be produced by successive deposition of the individual layers onto a suitable substrate.
  • all layers are prepared by solution processing.
  • at least one layer that does not contain the semiconductor A) may be coated by vapour phase deposition techniques known to those skilled in the art.
  • Suitable as substrate 1 are transparent carriers, such as glass or plastics films (for example polyesters, such as polyethylene terephthalate or polyethylene naphthalate, polycarbonate, polyacrylate, polysulphone, polyimide foil).
  • transparent and conducting materials are a) metal oxide, for example indium-tin oxide (ITO), tin oxide (NESA), etc. and b) semi-transparent metal films, for example Au, Pt, Ag, Cu, etc.
  • low molecular weight or oligomeric as well as polymeric materials may be used as light-emitting layer 5.
  • the substances are characterized by the fact that they are photoluminescing. Accordingly, suitable substances are for example fluorescent dyes and fluorescent products that are forming oligomers or are incorporated into polymers. Examples of such materials are coumarins, perylenes, anthracenes, phenanthrenes, stilbenes, distyryls, methines or metal complexes such as Alq 3 (tris(8-hydroxyquinolinato)aluminium), etc.
  • Suitable polymers include optionally substituted phenylenes, phenylene vinylenes or polymers with fluorescing segments in the polymer side chain or in the polymer backbone.
  • EP-A-532 798 A detailed list is given in EP-A-532 798 .
  • electron-injecting or hole-injecting layers (3 and/or 7) can be incorporated into the EL arrangements.
  • a large number of organic compounds that transport charges (holes and/or electrons) are described in the literature. Mainly low molecular weight substances are used, which are suitable for solution processing.
  • PEDOT poly-(3,4-ethylenedioxythiophene)
  • FIG. 1a shows the polarized optical micrograph of the crystalline organic film obtained by drop-casting of compound A1) from DMP and
  • FIG. 1b shows the micrograph of film obtained by drop-casting of compound A1) from EthAc.
  • the crystals obtained from the compositions of the invention show remarkably larger crystalline areas.
  • a 0.1 wt. % solution of A2) in a solvent according to table 1 is applied to a SiO 2 substrate and the solvent allowed to evaporate.
  • the semiconductor is stirred in the phthalate at 80°C for 60 minutes.
  • the crystals obtained from the compositions of the invention show remarkably larger crystalline areas.
  • Table 2 example solvent crystal length [ ⁇ m] crystal width [ ⁇ m] 2.1 DMP 35 5 2.2 DEP 100 50 2.3 DAP 60 50 C2.4 +) EthAc 20 #) 10 #) +) comparative, #) small polycrystalline to amorphous disconnected agglomerates
  • a 0.1 wt. % solution of A3) in a solvent according to table 1 is applied to a SiO 2 substrate and the solvent allowed to evaporate.
  • the semiconductor is stirred in the phthalate at 80°C for 60 minutes.
  • the crystals obtained from the compositions of the invention show remarkably larger crystalline areas.
  • Table 3 example solvent crystal length [ ⁇ m] crystal width [ ⁇ m] 3.1 DAP 200 250 C3.2 +) EthAc 20 #) 3 #) C3.3 +) Acac 20 #) 3 #) +) comparative, #) small polycrystalline to amorphous disconnected agglomerates
  • a 0.1 wt. % solution of A4) in a solvent according to table 1 is applied to a SiO 2 substrate and the solvent allowed to evaporate.
  • the semiconductor is stirred in the phthalate at 80°C for 60 minutes.
  • the crystals obtained from the compositions of the invention show remarkably larger crystalline areas.
  • Table 4 example solvent crystal length [ ⁇ m] crystal width [ ⁇ m] 4.1 DMP 500 200 4.2 DEP 1200 650 4.3 DAP 250 150 C4.3 +) EthAc 3 #) 2 #) +) comparative, #) small polycrystalline to amorphous disconnected agglomerates
  • Example 5 Drop-casting of A4) from DMP solution on a SiO 2 wafer
  • a 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in dimethyl phthalate for 1 h at 80°C and then stirred for further 30 minutes. The solution was allowed to cool to ambient temperature and was filtered through a 0.2 ⁇ m PTFE filter. Si/SiO 2 wafers from WRS Materials heavily p-doped with boron (550 to 600 ⁇ m thickness, 100 nm insulating dielectric layer of thermally oxidized silicon) were used as back gate substrate. 1 to 10 ⁇ L of solution was deposited onto the wafer on a hotplate at 60 to 90°C in a flow box.
  • a 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in a 1:9 mixture of dimethyl phthalate and acetylacetone for 1 h at 80°C and then stirred for further 30 minutes. The solution was allowed to cool to ambient temperature and was filtered through a 0.2 ⁇ m PTFE filter. Si/SiO 2 wafers from WRS Materials heavily p-doped with boron (550 to 600 ⁇ m thickness, 100 nm insulating dielectric layer of thermally oxidized silicon) were used as back gate substrate. 1 to 10 ⁇ L of solution was deposited onto the wafer on a hotplate at 60 to 90°C in a flow box.
  • Example 7 Drop-casting of A4) from a DMP solution on an Al 2 O 3 layer
  • a 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in dimethyl phthalate for 1 h at 80°C and then stirred for further 30 minutes. The solution was allowed to cool to ambient temperature and was filtered through a 0.2 ⁇ m PTFE filter. Si/SiO 2 wafers from WRS Materials heavily p-doped with boron (550 to 600 ⁇ m thickness, 30 nm insulating dielectric layer of Al 2 O 3 ) were used as back gate substrate. 1 to 10 ⁇ L of solution was deposited onto the wafer on a hotplate at 60 to 90°C in a flow box. After complete evaporation of solvent the sample was put in a vacuum oven for 1h at 70°C to eliminate residual solvent trapped in the film.
  • Gold contacts (Umicore, 99.99%) were deposited at a base pressure of 6 x 10 -6 mbar through a kapton shadow mask via thermal evaporation yielding a channel width (W) of 200 ⁇ m and channel length (L) of 100 ⁇ m. Electrical characterization was conducted in a dark box under ambient conditions using an Agilent 4145C Semiconductor Parameter Analyzer.
  • Example 8 Drop-casting of A4) from a DMP solution on Al 2 O 3 after surface modification
  • a 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in dimethyl phthalate for 1 h at 80°C and then stirred for further 30 minutes. The solution was allowed to cool to ambient temperature and was filtered through a 0.2 ⁇ m PTFE filter. Si/SiO 2 wafers from WRS Materials heavily p-doped with boron (550 to 600 ⁇ m thickness, 30 nm insulating dielectric layer of Al 2 O 3 ) were used as back gate substrate. Prior to material deposition, a surface treatment was conducted; the substrate was exposed to O 2 plasma for 300 seconds.
  • 4-Ethoxyphenylphosphonic acid (CAS 69387-02-6 ) was dissolved in isopropanol at a concentration of 2 mMol (typically 4 mg/10 ml) and stirred at room temperature for 20 minutes.
  • the substrate was immersed in the solution for 1 hour in a covered petri dish. After subsequent rinsing with isopropanol and drying under N 2 , the substrates were baked at 150°C on a hotplate. 1 to 10 ⁇ L of solution was deposited onto the wafer on a hotplate at 60 to 90°C in a flow box. After complete evaporation of solvent the sample was put in a vacuum oven for 1 h at 70°C to eliminate residual solvent trapped in the film.
  • Gold contacts (Umicore, 99.99%) were deposited at a base pressure of 6 x 10 -6 mbar through a kapton shadow mask via thermal evaporation yielding a channel width (W) of 200 ⁇ m and channel length (L) of 100 ⁇ m. Electrical characterization was conducted in a dark box under ambient conditions using an Agilent 4145C Semiconductor Parameter Analyzer.
  • a 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in dimethyl phthalate for 1 h at 80°C and then stirred for further 30 minutes. The solution was allowed to cool to ambient temperature and was filtered through a 0.2 ⁇ m PTFE filter. A polyethylene terephthalate (PET) foil (Hostaphan 4600GN 175 from Mitsubishi Polyester Film) was used as substrate. Gold contacts (Umicore, 99.99%) were deposited at a base pressure of 6 x 10 -6 mbar through a kapton shadow mask via thermal evaporation yielding a channel width (W) of 500 ⁇ m and channel length (L) of 50 ⁇ m.
  • PET polyethylene terephthalate
  • Example 10 Inkjet printing of A4) from DMP solution on a SiO 2 wafer
  • a 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in dimethyl phthalate for 1 h at 80°C and then stirred for further 30 minutes. The solution was allowed to cool to ambient temperature and was filtered through a 0.2 ⁇ m PTFE filter. Si/SiO 2 wafers from WRS Materials heavily p-doped with boron (550 to 600 ⁇ m thickness, 100 nm insulating dielectric layer of thermally oxidized silicon) were used as back gate substrate. The ink was printed with a Dimatix DMP2831 printer at a drop space of 20 ⁇ m with the nozzle at 35°C and the printing plate at room temperature.
  • the printed substrates were dried 5 h at 60°C in ambient air followed by a second drying step for one hour at 110°C in a vacuum oven (about 5 mbar pressure). After complete evaporation of solvent the sample was put in a vacuum oven for 1 h at 70°C to eliminate residual solvent trapped in the film.
  • Gold contacts (Umicore, 99.99%) were deposited at a base pressure of 6 x 10 -6 mbar through a kapton shadow mask via thermal evaporation yielding a channel width (W) of 200 ⁇ m and channel length (L) of 100 ⁇ m. Electrical characterization was conducted in a dark box under ambient conditions using an Agilent 4145C Semiconductor Parameter Analyzer.
  • Example 11 Inkjet printing of A4) from a DMP solution on Al 2 O 3 after surface modification
  • a 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in dimethyl phthalate for 1 h at 80°C and then stirred for further 30 minutes. The solution was allowed to cool to ambient temperature and was filtered through a 0.2 ⁇ m PTFE filter. Si/SiO 2 wafers from WRS Materials heavily p-doped with boron (550 to 600 ⁇ m thickness, 30 nm insulating dielectric layer of Al 2 O 3 ) were used as back gate substrate. Prior to material deposition, a surface treatment was conducted; the substrate was exposed to O 2 plasma for 300 seconds.
  • 4-Ethoxyphenylphosphonic acid ( CAS 69387-02-6 ) was dissolved in isopropanol at a concentration of 2 mMol (typically 4 mg/10 ml) and stirred at room temperature for 20 minutes.
  • the substrate was immersed in the solution for 1 hour in a covered petri dish. After subsequent rinsing with isopropanol and drying under N2, the substrates were baked at 150°C on a hotplate.
  • the ink was printed with a Dimatix DMP2831 printer at a drop space of 20 ⁇ m with the nozzle at 35°C and the printing plate at room temperature.
  • the printed substrates were dried 5 h at 60°C in ambient air followed by a second drying step for one hour at 110°C in a vacuum oven (about 5 mbar pressure). After complete evaporation of solvent the sample was put in a vacuum oven for 1 h at 70°C to eliminate residual solvent trapped in the film.
  • Gold contacts (Umicore, 99.99%) were deposited at a base pressure of 6E-6 mbar through a kapton shadow mask via thermal evaporation yielding a typical channel W/L of 200 ⁇ m/100 ⁇ m. Electrical characterization was conducted in a dark box under ambient conditions using an Agilent 4145C Semiconductor Parameter Analyzer.
  • Example 12 Drop-casting of A4) from a DMP solution on a SiO 2 wafer using a poly(methyl methacrylate)/trimethylolpropane triacrylate bottom-gate dielectric
  • a 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in dimethyl phthalate for 1 h at 80°C and then stirred for further 30 minutes. The solution was allowed to cool to ambient temperature and was filtered through a 0.2 ⁇ m PTFE filter. Si/SiO 2 wafers from WRS Materials heavily p-doped with boron (550 to 600 ⁇ m thickness, 100 nm insulating dielectric layer of thermally oxidized silicon) with a UV-crosslinked polymer dielectric were used as backgate substrate. The dielectric properties are summarized in the table below.
  • Example 13 Inkjet printing of A3) from DMP solution on Al 2 O 3
  • a 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in dimethyl phthalate for 1 h at 80°C and then stirred for further 30 minutes. The solution was allowed to cool to ambient temperature and was filtered through a 0.2 ⁇ m PTFE filter. Si/SiO 2 wafers from WRS Materials heavily p-doped with boron (550 to 600 ⁇ m thickness, 30 nm insulating dielectric layer of Al 2 O 3 ) were used as back gate substrate. The ink was printed with a Dimatix DM P2831 printer at a drop space of 20 ⁇ m with the nozzle at 35°C and the printing plate at room temperature.
  • the printed substrates were dried 5 h at 60°C in ambient air followed by a second drying step for one hour at 110°C in a vacuum oven (about 5 mbar pressure). After complete evaporation of solvent the sample was put in a vacuum oven for 1 h at 70°C to eliminate residual solvent trapped in the film.
  • Gold contacts (Umicore, 99.99%) were deposited at a base pressure of 6 x 10 -6 mbar through a kapton shadow mask via thermal evaporation yielding a channel width (W) of 200 ⁇ m and channel length (L) of 100 ⁇ m. Electrical characterization was conducted in a dark box under ambient conditions using an Agilent 4145C Semiconductor Parameter Analyzer.
  • Degenerately doped silicon wafers (wafers from WRS Materials heavily p-doped with boron, 550 - 600 ⁇ m thickness) coated with a 240 nm thermally grown silicon dioxide were used as substrate. They were subjected to 2 min oxygen plasma treatment (100W, 20 standard cubic centimeters per minute (sccm) gas flow) and subsequently immersed into a 0.2 vol% solution of octadecyltrichlorosilane (OTS) in toluene for 17 minutes at room temperature. Subsequently the sample was removed from the solution, rinsed with toluene and baked for 30 min at 90 °C.
  • oxygen plasma treatment 100W, 20 standard cubic centimeters per minute (sccm) gas flow
  • OTS octadecyltrichlorosilane
  • a 0.5-1 mm thick layer of polydimethylsiloxane (PDMS) comprising holes with a diameter of 7.3 mm was placed onto the hydrophobic substrate that was subsequently subjected to a 5 minutes treatment with air plasma.
  • This plasma burns away the hydrophobic monolayer in the locations of the holes of the PDMS layer exposing the bare, more hydrophilic SiO 2 surface.
  • Table 7 List of solvent mixtures and solvent-polymer mixtures tested example no. solvent mixture, polymer-solvent mixture Viscosity [mPas] Surface tension [mN/m] crystal form 21 DMP: PS (1.5 mg PS / 1g DMP) 20 not measured thin 22 DEP: PS (2.3 mg PS / 1g DEP) 19 not measured thin 23 DMP: PS (wire-bar coated) (1.5 mg PS / 1g DMP) 20 not measured thin 24 DEP: PS (wire-bar coated) (2.3 mg PS / 1g DEP) 19 not measured thin
  • TDPA tetradecyl phosphonic acid
  • a layer of PDMS having a thickness of 0.5-1 mm and comprising holes with a diameter of 7.3 mm was placed onto the hydrophobic substrate that was subsequently subjected to a 5 minutes treatment with air plasma.
  • This plasma burns away the hydrophobic monolayer in the locations of the holes of the PDMS layer exposing the bare, more hydrophilic Al 2 O 3 surface.
  • the resulting plasma-treated hydrophilic areas of the substrate were then treated with 4-ethoxyphenylphosphonic acid (EPPA) in the same manner as described above for the TDPA SAM. This process yields a hydrophilic EPPA SAM in the circular regions that had been subjected to the second plasma treatment step.
  • the surface energy of the EPPA-treated areas was determined to be 36 mN/m.
  • 0.1 wt% of semiconductor powder was dissolved in the respective solvent for 1h at 80°C under constant shaking. After cooling the solution to room temperature it was filtered through a 0.2 ⁇ m PTFE filter.
  • solvent mixtures were used, first the semiconductor was dissolved in the respective individual solvent, subjected to shaking at 80°C for 1 h, filtered and subsequently mixed to the respective solvent ratios. 1 ⁇ L of the organic semiconductor solution was drop casted with a pipette onto the hydrophilic EPPA areas at an elevated substrate temperature (70 °C, substrate placed on hotplate). After several hours to 2 days of drying at 70°C the samples were transferred to a vacuum oven and heated to 60°C to 90 °C for additional 3 hours to completely remove residual solvent. Optical images were recorded under a polarized microscope in reflection mode.
  • a crystalline material of semiconductor (A4) was prepared using a solvent mixture of DMP and toluene (wt. ratio 1:3).
  • the solids content of the semiconductor solution was 0.1 wt.% and drying was performed at 70°C on a hotplate.
  • Figure 11 shows the polarized optical micrograph of the obtained crystalline organic film.
  • the combination of DMP with toluene as a solvent mixture according to the invention leads to a semiconductor material having a large area of thin connected continuous crystals.
  • a crystalline material of semiconductor (A4) was prepared using acetylacetone as solvent.
  • the solids content of the semiconductor solution was 0.1 wt.-% and drying was performed at 70°C on a hotplate.
  • Figure 12 shows the polarized optical micrograph of the obtained crystalline organic film.
  • the use of a solvent that is not a solvent (B) in the sense of the invention leads to a semiconductor material having thick disconnected crystals.
  • a crystalline material of semiconductor (A4) was prepared using toluene as solvent.
  • the solids content of the semiconductor solution was 0.1 wt.-% and drying was performed at 30°C on a hotplate.
  • Figure 13 shows the polarized optical micrograph of the obtained crystalline organic film.
  • Example 28 Drop-casting of A4) from a DMP:Toluene (1:3) mixture on Al 2 O 3 after surface modification
  • a 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in dimethyl phthalate for 1 h at 80°C and then stirred for further 30 minutes.
  • a second 0.1 wt.-% solution of the semiconductor material A4) was prepared by dissolution in toluene for 1 h at 80°C and then stirred for further 30 minutes.
  • the two solutions were mixed at a weight ratio of 1 (DMP) to 3 (toluene).
  • the combined solution was allowed to cool to ambient temperature and was filtered through a 0.2 ⁇ m PTFE filter.
  • Silicon wafers from WRS Materials (heavily p-doped with boron, 550 to 600 ⁇ m thickness) coated with Al 2 O 3 (30nm thick, grown via atomic layer deposition) were subjected to a 2 minutes treatment with oxygen plasma (100W, 20 sccm gas flow) and subsequently immersed into a 1.5 mM solution of tetradecyl phosphonic acid (TDPA) in isopropanol for 1 hour at room temperature. Subsequently the sample was removed from the solution, rinsed with isopropanol and baked for 5 min at 120 °C on a hotplate.
  • TDPA tetradecyl phosphonic acid
  • This procedure yields a hydrophobic self-assembled monolayer (SAM) on the Al 2 O 3 surface with a surface energy of 22 mN/m (surface energy determined via water contact angle measurement).
  • SAM self-assembled monolayer
  • a layer of PDMS having a thickness of 0.5-1 mm and comprising holes with a diameter of 8 mm was placed onto the hydrophobic substrate that was subsequently subjected to a 2 minutes treatment with air plasma (100W, 20 sccm gas flow). This plasma burns away the hydrophobic monolayer in the locations of the holes of the PDMS layer exposing the bare, more hydrophilic Al 2 O 3 surface. 1 to 10 ⁇ L of solution was deposited onto the wafer on a hotplate at 70°C in a flow box.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Thin Film Transistor (AREA)
  • Photovoltaic Devices (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electroluminescent Light Sources (AREA)
  • Plural Heterocyclic Compounds (AREA)

Claims (15)

  1. Utilisation d'une composition comprenant
    A) au moins un semi-conducteur organique choisi parmi des composés de type rylène de la formule générale (I.a)
    Figure imgb0089
     n étant 1, 2, 3 ou 4,
    Ra et Rb étant choisis indépendamment l'un de l'autre parmi hydrogène et alkyle, alcényle, alcadiényle, alcynyle, cycloalkyle, bicycloalkyle, cycloalcényle, hétérocycloalkyle, aryle et hétéroaryle, en chaque cas non substitué ou substitué,
    les radicaux Rn1, Rn2, Rn3 et Rn4 étant choisis indépendamment l'un de l'autre parmi hydrogène, F, Cl, Br, I, CN, hydroxy, mercapto, nitro, cyanato, thiocyanato, formyle, acyle, carboxy, carboxylate, alkylcarbonyloxy, carbamoyle, alkylaminocarbonyle, dialkylaminocarbonyle, sulfo, sulfonate, sulfoamino, sulfamoyle, alkylsulfonyle, arylsulfonyle, amidino, NE1E2, où E1 et E2 sont chacun indépendamment choisis parmi hydrogène, alkyle, cycloalkyle, hétérocycloalkyle, aryle et hétaryle ;
    alkyle, alcoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyle, cycloalcoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, hétérocycloalkyle, hétérocycloalcoxy, hétérocycloalkylthio, (monohétérocycloalkyl)amino, (dihétérocycloalkyl)amino, aryle, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hétaryle, hétaryloxy, hétarylthio, (monohétaryl)amino et (dihétaryl)amino, en chaque cas non substitué ou substitué, et
    B) au moins un composé qui est liquide à 20 °C et 1 013 mbars, choisi parmi des composés de la formule (II)

            Rc-X1-A-X2-Rd     (II)

    A étant un carbocycle ou hétérocycle aliphatique ou aromatique, non substitué ou substitué, à 5 à 8 chaînons,
    X1 et X2 étant *-(C=O)-O-, où * est le point de liaison au carbocycle ou hétérocycle aliphatique ou aromatique ;
    et
    Rc et Rd étant indépendamment choisis parmi C1-C12-alkyle et C2-C12-alcényle, non ramifiés et ramifiés ;
    pour la production d'un matériau semi-conducteur, préférablement d'un matériau semi-conducteur dans des appareils électroniques organiques ou des appareils photovoltaïques organiques.
  2. Utilisation selon la revendication 1, Ra et Rb étant choisis indépendamment l'un de l'autre parmi hydrogène, C1-C30-alkyle linéaire, C3-C30-alkyle ramifié, perfluoro-C1-C30-alkyle, 1H, 1H-perfluoro-C2-C30-alkyle, 1H, 1H, 2H, 2H-perfluoro-C3-C30-alkyle, un radical de la formule G.1, un radical de la formule G.2 et un radical de la formule G.3
    Figure imgb0090
     où
    # représente le site de liaison à un atome d'azote,
    B s'il est présent, est un groupe C1-C10-alkylène qui peut être interrompu par un ou plusieurs groupes non adjacents qui sont choisis parmi -O- et -S-,
    y est 0 ou 1,
    Rm est indépendamment l'un de l'autre choisi parmi C1-C30-alkyle, C1-C30-fluoroalkyle, fluor, chlore, brome, NE3E4, nitro et cyano, où E3 et E4, indépendamment l'un de l'autre, sont hydrogène, alkyle, cycloalkyle, hétérocycloalkyle, aryle ou hétaryle,
    Rn est indépendamment l'un de l'autre choisi parmi C1-C30-alkyle,
    x dans les formules G.2 et G.3 est 1, 2, 3, 4 ou 5.
  3. Utilisation selon l'une quelconque des revendications précédentes, Ra et Rb étant choisis parmi des radicaux des formules générales (III.1), (III.2) et (III.3)
    Figure imgb0091
     # étant un site de liaison, et
    dans la formule (III.1) Re et Rf étant indépendamment choisis parmi C1-C27-alkyle, où la somme des atomes de carbone des radicaux Re et Rf est un entier de 2 à 28, dans la formule (III. 2) Rg et Rh étant indépendamment choisis parmi C1-C28-alkyle, où la somme des atomes de carbone des radicaux Rg et Rh est un entier de 2 à 29, dans la formule (III.3) Ri, Rk et Rl étant indépendamment choisis parmi C1-C27-alkyle, où la somme des atomes de carbone des radicaux Ri, Rk et Rl est un entier de 3 à 29.
  4. Utilisation selon l'une quelconque des revendications précédentes, Ra et Rb possédant la même signification.
  5. Utilisation selon l'une quelconque des revendications précédentes, le composant A) étant choisi parmi des composés de la formule générale (I.a1)
    Figure imgb0092
     Ra et Rb étant tels que définis dans l'une quelconque des revendications 1 à 4,
    R12 et R23 étant indépendamment choisis parmi F, Cl, Br, CN, et
    R11, R13, R14, R21, R22 et R24 étant hydrogène.
  6. Utilisation selon l'une quelconque des revendications précédentes, le composé de la formule générale (II) étant choisi parmi des composés des formules (II.1), (II.2), (II.3), (II.4) et (II.5)
    Figure imgb0093
    Figure imgb0094
    Figure imgb0095
     X1 et X2 étant *-(C=O)-O-, où * est le point de liaison au carbocycle ou hétérocycle aliphatique ou aromatique ;
    et
    Rc et Rd étant indépendamment choisis parmi C1-C12-alkyle et C2-C12-alcényle, non ramifiés et ramifiés.
  7. Utilisation selon l'une quelconque des revendications précédentes, le composé de la formule II étant choisi parmi le phtalate de diméthyle, le phtalate de diéthyle, le phtalate de di(n-propyle), le phtalate de di(n-butyle), le phtalate de diallyle et des mélanges correspondants.
  8. Utilisation selon l'une quelconque des revendications 1 à 7, le semi-conducteur organique A) possédant une solubilité dans le composant B) à 20 °C d'au moins 0,01 mg/ml, préférablement d'au moins 0,05 mg/ml.
  9. Utilisation selon l'une quelconque des revendications précédentes, comprenant un cosolvant C) choisi parmi des solvants organiques différents du composant B) et des mélanges de solvants organiques différents du composant B), le cosolvant C) étant choisi parmi
    - des hydrocarbures aliphatiques, cycloaliphatiques et aromatiques,
    - des éthers aromatiques,
    - des éthers aliphatiques à chaîne ouverte, des polyéthers, des éther-alcools et des éthers cycliques,
    - des cétones,
    - des esters,
    - des alcools aliphatiques et cycloaliphatiques,
    - des alcools à base de benzène,
    - des composés aromatiques halogénés,
    - des thiophénols et des benzènes substitués par alkylthio,
    - des composés aromatiques comprenant un groupe phényle condensé à un groupe cyclohétéroalkyle à 5, 6 ou 7 chaînons,
    - des composés hétéroaryle à 5 chaînons et des composés hétéroaryle à 5 chaînons benzo-condensés,
    - des acides carboxyliques aromatiques,
    - des aldéhydes aromatiques,
    - des composés de type benzène substitué par trifluorométhyle,
    - des composés de type benzène substitué par cyano ou substitué par isocyano,
    - des composés de type benzène substitué par nitro,
    - des phénylsulfones,
    - des composés hétéroaryle à 6 chaînons et des composés hétéroaryle à 6 chaînons benzocondensés,
    - des composés hétéroaryle à 5 chaînons et des composés hétéroaryle à 5 chaînons benzocondensés,
    - des solvants polaires aprotiques et
    - des mélanges correspondants.
  10. Utilisation selon la revendication 9 dans laquelle le semi-conducteur organique A) possède une solubilité dans le mélange de composants B) et C) à 20 °C d'au moins 0,01 mg/ml, préférablement d'au moins 0,1 mg/ml.
  11. Utilisation selon l'une quelconque des revendications précédentes qui contient un additif de modification de la viscosité, préférablement choisi parmi des polymères diélectriques et des polymères semi-conducteurs, en particulier un polystyrène.
  12. Procédé pour la préparation d'un dispositif électronique, d'un dispositif optique, d'un dispositif optoélectronique ou d'un capteur, comprenant :
    (a) la mise à disposition d'une composition comprenant A) au moins un semi-conducteur organique et B) au moins un composé qui est liquide à 20 °C et 1 013 mbars, tel que défini dans l'une quelconque des revendications 1 à 11,
    (b) l'application de la composition mise à disposition dans l'étape (a) sur au moins une partie de la surface d'un substrat pour permettre le dépôt de l'au moins un semi-conducteur organique sur le substrat.
  13. Procédé selon la revendication 12, dans lequel dans l'étape (b) l'application de la composition mise à disposition dans l'étape (a) sur au moins une partie de la surface du substrat est réalisée par impression.
  14. Procédé selon l'une quelconque des revendications 12 et 13, la surface du substrat qui est employé pour l'application de la composition semi-conductrice mise à disposition dans l'étape (a) étant revêtue avec un diélectrique ; et/ou
    la surface du substrat ou, s'il est présent, le revêtement diélectrique sur le substrat, étant soumis(e) à une modification de surface avant l'application de la composition semi-conductrice mise à disposition dans l'étape (a), le composé utilisé pour la modification de surface étant choisi parmi des silanes, des acides phosphoniques, des acides carboxyliques, des acides hydroxamiques, des amines, des phosphines, des composés comprenant du soufre et des mélanges correspondants.
  15. Procédé selon l'une quelconque des revendications 12 à 14, le dispositif étant choisi parmi des transistors organiques à effet de champ, des agencements électroluminescents, des cellules solaires organiques et des photodétecteurs.
EP15833336.9A 2014-08-18 2015-08-17 Composition à semi-conducteurs organiques comprenant un milieu liquide Active EP3183757B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14181269 2014-08-18
PCT/IB2015/056248 WO2016027217A1 (fr) 2014-08-18 2015-08-17 Composition à semi-conducteurs organiques comprenant un milieu liquide

Publications (3)

Publication Number Publication Date
EP3183757A1 EP3183757A1 (fr) 2017-06-28
EP3183757A4 EP3183757A4 (fr) 2018-04-18
EP3183757B1 true EP3183757B1 (fr) 2022-05-04

Family

ID=51399515

Family Applications (2)

Application Number Title Priority Date Filing Date
EP15833336.9A Active EP3183757B1 (fr) 2014-08-18 2015-08-17 Composition à semi-conducteurs organiques comprenant un milieu liquide
EP15833858.2A Active EP3183250B1 (fr) 2014-08-18 2015-08-17 Procédé de préparation de matériau semi-conducteur organique cristallin

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP15833858.2A Active EP3183250B1 (fr) 2014-08-18 2015-08-17 Procédé de préparation de matériau semi-conducteur organique cristallin

Country Status (7)

Country Link
US (2) US10224485B2 (fr)
EP (2) EP3183757B1 (fr)
JP (2) JP6861625B2 (fr)
KR (2) KR102366484B1 (fr)
CN (2) CN107004768B (fr)
TW (2) TWI680127B (fr)
WO (2) WO2016027218A1 (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015128779A1 (fr) * 2014-02-25 2015-09-03 Basf Se Hétéroacènes pour l'électronique organique
JP6274529B2 (ja) * 2015-02-09 2018-02-07 富士フイルム株式会社 有機半導体素子及びその製造方法、有機半導体膜形成用組成物、並びに、有機半導体膜の製造方法
GB2554404A (en) * 2016-09-26 2018-04-04 Sumitomo Chemical Co Solvent systems for preparation of photosensitive organic electronic devices
CN110198995B (zh) * 2017-01-19 2021-10-08 日产化学株式会社 用于形成微细相分离图案的自组装化膜形成用组合物
CN108461640B (zh) * 2018-03-16 2020-01-31 中国科学院长春应用化学研究所 晶态有机电致发光二极管及其应用
JP2021082619A (ja) * 2018-03-16 2021-05-27 国立大学法人大阪大学 ｎ型有機半導体材料及びそれを含有する有機半導体膜並びに有機薄膜トランジスタ
GB2575327A (en) * 2018-07-06 2020-01-08 Sumitomo Chemical Co Organic photodetector
KR102447937B1 (ko) 2018-07-23 2022-09-27 주식회사 엘지화학 2-시아노에틸기 함유 중합체의 제조 방법
KR101910157B1 (ko) * 2018-08-06 2018-10-19 영창케미칼 주식회사 유무기 하이브리드 포토레지스트 공정액 조성물
US11702557B2 (en) * 2018-09-19 2023-07-18 Daicel Corporation Ink composition for manufacturing organic semiconductor device
EP3664171B1 (fr) * 2018-12-06 2021-05-12 Flexterra, Inc. Transistor à couche mince comprenant des matériaux semi-conducteurs organiques
CN109776533B (zh) * 2019-02-12 2020-10-30 宁波卢米蓝新材料有限公司 一种萘二酰亚胺衍生物及其制备方法和应用
EP3958335A4 (fr) * 2019-04-15 2023-02-01 Daicel Corporation Composition d'encre pour production de dispositif à semi-conducteur organique
WO2021033738A1 (fr) 2019-08-22 2021-02-25 富士フイルム株式会社 Composition durcissable, article durci, élément optique et lentille
TWI732389B (zh) * 2019-12-19 2021-07-01 明基材料股份有限公司 一種優化原子層沉積的方法
JP7464397B2 (ja) * 2020-01-31 2024-04-09 保土谷化学工業株式会社 ペリレン誘導体化合物、該化合物を用いた有機半導体用組成物、該有機半導体用組成物を用いた有機薄膜トランジスタ
US20230274930A1 (en) * 2020-07-09 2023-08-31 Basf Se Composition Comprising a Siloxane and an Alkane for Avoiding Pattern Collapse When Treating Patterned Materials with Line-Space Dimensions of 50 NM or Below
CN112432977B (zh) * 2020-11-18 2022-04-12 中国科学院上海微系统与信息技术研究所 一种有机场效应晶体管气体传感器及其制备方法
CN116444519B (zh) * 2023-03-29 2025-07-18 华南理工大学 一类具有魔角堆积结构特征的苝酰亚胺发光晶体及其应用
CN116943699B (zh) * 2023-06-06 2025-09-19 浙江恒逸石化研究院有限公司 一种对苯二甲酸二甲酯加氢制备1,4-环己烷二甲酸二甲酯的催化剂及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4678608A (en) * 1985-04-15 1987-07-07 American Cyanamid Company Chemiluminescent composition
US20030111649A1 (en) * 2001-10-22 2003-06-19 Park Koon Ha Chemiluminescent composition for emitting red light
US20080308776A1 (en) * 2007-06-14 2008-12-18 Bindra Perminder S Chemiluminescent compositions and methods of making and using thereof

Family Cites Families (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1031323B (de) 1956-02-14 1958-06-04 Norddeutsche Affinerie Verfahren zur Duengung mit Spurenelementen
DE1945359B2 (de) 1969-09-08 1973-05-10 Verfahren zur gewinnung von estern
DE2612355C3 (de) 1976-03-24 1983-11-17 Basf Ag, 6700 Ludwigshafen Verfahren zur Abtrennung von Katalysatoren aus rohen Weichmacherestern
US4461922A (en) 1983-02-14 1984-07-24 Atlantic Richfield Company Solar cell module
US4539507A (en) 1983-03-25 1985-09-03 Eastman Kodak Company Organic electroluminescent devices having improved power conversion efficiencies
US4720432A (en) 1987-02-11 1988-01-19 Eastman Kodak Company Electroluminescent device with organic luminescent medium
US4769292A (en) 1987-03-02 1988-09-06 Eastman Kodak Company Electroluminescent device with modified thin film luminescent zone
US5126214A (en) 1989-03-15 1992-06-30 Idemitsu Kosan Co., Ltd. Electroluminescent element
JP3069139B2 (ja) 1990-03-16 2000-07-24 旭化成工業株式会社 分散型電界発光素子
US5324853A (en) 1993-01-19 1994-06-28 Exxon Chemical Patents Inc. Process for the production of plasticizer and polyolesters
DE19721347B9 (de) 1997-05-22 2005-09-29 Celanese Chemicals Europe Gmbh Verfahren zur Herstellung von Esterweichmachern
WO1999032427A1 (fr) 1997-12-19 1999-07-01 Basf Aktiengesellschaft Procede d'hydrogenation d'acides polycarboxyliques de benzene ou de leurs derives a l'aide d'un catalyseur a macropores
US6198091B1 (en) 1998-08-19 2001-03-06 The Trustees Of Princeton University Stacked organic photosensitive optoelectronic devices with a mixed electrical configuration
US6198092B1 (en) 1998-08-19 2001-03-06 The Trustees Of Princeton University Stacked organic photosensitive optoelectronic devices with an electrically parallel configuration
US6451415B1 (en) 1998-08-19 2002-09-17 The Trustees Of Princeton University Organic photosensitive optoelectronic device with an exciton blocking layer
EP1449238B1 (fr) 1999-05-13 2006-11-02 The Trustees Of Princeton University Dispositifs electroluminescents organiques a tres haute performance utilisant l'electrophosphorescence
DE10056179A1 (de) 2000-11-13 2002-05-29 Basf Ag Verfahren zur Herstellung von Estern mehrbasiger Säuren
DE10128242A1 (de) 2001-06-11 2002-12-12 Basf Ag Verfahren zur Hydrierung organischer Verbindungen
DE10129129C1 (de) 2001-06-16 2002-12-05 Celanese Chem Europe Gmbh Verfahren zur Herstellung von Cyclohexandicarbonsäureestern
DE10146869A1 (de) 2001-09-24 2003-04-24 Oxeno Olefinchemie Gmbh Alicyclische Polycarbonsäureestergemische mit hohem trans-Anteil und Verfahren zu deren Herstellung
DE10146848A1 (de) 2001-09-24 2003-04-24 Oxeno Olefinchemie Gmbh Gemisch alicyclischer Polycarbonsäureester mit hohem cis-Anteil
US20030097010A1 (en) 2001-09-27 2003-05-22 Vogel Dennis E. Process for preparing pentacene derivatives
AU2002327747A1 (en) 2001-09-27 2003-04-07 3M Innovative Properties Company Substituted pentacene semiconductors
US7102154B2 (en) * 2002-02-08 2006-09-05 Dai Nippon Printing Co. Ltd Organic semiconductor structure, process for producing the same, and organic semiconductor device
DE10232868A1 (de) 2002-07-19 2004-02-05 Oxeno Olefinchemie Gmbh Feinporiger Katalysator und Verfahren zur Hydrierung von aromatischen Verbindungen
US6911716B2 (en) 2002-09-09 2005-06-28 Lucent Technologies, Inc. Bipolar transistors with vertical structures
DE10338550A1 (de) 2003-08-19 2005-03-31 Basf Ag Übergangsmetallkomplexe mit Carbenliganden als Emitter für organische Licht-emittierende Dioden (OLEDs)
US7592539B2 (en) 2003-11-07 2009-09-22 The Trustees Of Princeton University Solid state photosensitive devices which employ isolated photosynthetic complexes
EP1749316B1 (fr) 2004-01-26 2016-06-29 Northwestern University Semi-conducteurs de type perylene n et dispositifs associes
US20050224905A1 (en) 2004-04-13 2005-10-13 Forrest Stephen R High efficiency organic photovoltaic cells employing hybridized mixed-planar heterojunctions
US7605394B2 (en) 2004-12-23 2009-10-20 Northwestern University Siloxane-polymer dielectric compositions and related organic field-effect transistors
KR20080103076A (ko) 2006-02-17 2008-11-26 바스프 에스이 플루오르화 릴렌테트라카르복실산 유도체 및 이의 용도
EP1843407A1 (fr) 2006-04-07 2007-10-10 Basf Aktiengesellschaft Derivés d'acides rylenetetracarboxyliques et ses utilisations
US7569693B2 (en) 2006-06-12 2009-08-04 Northwestern University Naphthalene-based semiconductor materials and methods of preparing and use thereof
EP2077590B1 (fr) 2006-10-20 2013-06-19 Nippon Kayaku Kabushiki Kaisha Transistor à effet de champ
EP2086974B1 (fr) 2006-11-17 2013-07-24 Polyera Corporation Matériaux semi-conducteurs à base de diimide et procédés de préparation et d'utilisation de ceux-ci
CN101796621B (zh) * 2007-09-03 2012-06-20 富士胶片株式会社 制备有机半导体化合物的单晶薄膜的方法
KR20100065363A (ko) * 2007-09-12 2010-06-16 후지필름 가부시키가이샤 치환기 탈리 화합물의 제조 방법, 유기 반도체막 및 그 제조 방법
TWI439461B (zh) * 2008-02-05 2014-06-01 Basf Se 苝半導體及其製備方法與用途
WO2009109273A1 (fr) 2008-03-06 2009-09-11 Merck Patent Gmbh Formulation de semi-conducteur organique
JP5428104B2 (ja) 2008-05-23 2014-02-26 日本化薬株式会社 有機半導体組成物
US9512354B2 (en) * 2008-06-06 2016-12-06 Basf Se Chlorinated naphthalenetetracarboxylic acid derivatives, preparation thereof and use thereof in organic electronics
DE102009039102B4 (de) 2009-08-27 2022-01-27 Wdt-Wolz-Dental-Technik Gmbh Verfahren zur Herstellung von Zahnteilen aus Dentalmetallpulver
DE102009028976A1 (de) 2009-08-28 2011-03-03 Evonik Oxeno Gmbh Ester der 2,5-Furandicarbonsäure mit isomeren Decanolen und ihre Verwendung
CN102714276B (zh) * 2009-10-29 2016-06-01 大日精化工业株式会社 有机半导体材料、有机半导体薄膜以及有机薄膜晶体管
JP5745538B2 (ja) 2009-12-15 2015-07-08 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 芳香族化合物水素化用触媒とその方法
CN102668151B (zh) 2009-12-23 2015-06-17 默克专利有限公司 包含有机半导体化合物的组合物
WO2011128035A1 (fr) * 2010-04-12 2011-10-20 Merck Patent Gmbh Composition et procédé pour la préparation de dispositifs électroniques organiques
EP2659528B1 (fr) * 2010-12-30 2018-12-12 Basf Se Semi-conducteurs à base de pérylène et procédés de préparation et d'utilisation de ceux-ci
DE102011004676A1 (de) 2011-02-24 2012-08-30 Evonik Oxeno Gmbh Pentylester der Furandicarbonsäure
DE102011004677A1 (de) 2011-02-24 2012-08-30 Evonik Oxeno Gmbh Heptylester der Furandicarbonsäure
KR102072538B1 (ko) 2012-05-07 2020-02-03 바스프 에스이 유기 전자장치를 위한 페나센 화합물
KR102015162B1 (ko) 2012-06-12 2019-08-27 주식회사 다이셀 유기 트랜지스터 제조용 용제 또는 용제 조성물
GB201210858D0 (en) * 2012-06-19 2012-08-01 Cambridge Display Tech Ltd Method
US9293711B2 (en) 2012-08-09 2016-03-22 Polyera Corporation Organic semiconductor formulations
JP5964703B2 (ja) * 2012-09-10 2016-08-03 Dic株式会社 有機半導体材料、及び有機トランジスタ
TWI535726B (zh) * 2012-09-10 2016-06-01 迪愛生股份有限公司 苯并噻吩苯并噻吩衍生物、有機半導體材料及有機電晶體
KR101781708B1 (ko) 2012-12-03 2017-09-25 바스프 에스이 유기 전자기기를 위한 헤테로아센 화합물
JP2014139143A (ja) * 2013-01-21 2014-07-31 Idemitsu Kosan Co Ltd ジチエノフェナントレン化合物、当該化合物を含む有機薄膜トランジスタ用組成物、及び有機薄膜トランジスタ
US20140218452A1 (en) * 2013-02-05 2014-08-07 Hallyuen Holdings Ltd. Inkjet printing systems for permanent printing on nonporous surfaces
JP2014170857A (ja) * 2013-03-04 2014-09-18 Idemitsu Kosan Co Ltd 有機半導体溶液、当該有機半導体溶液を用いた有機半導体インク
JP6415274B2 (ja) * 2013-12-26 2018-10-31 キヤノン株式会社 電子写真感光体、プロセスカートリッジおよび電子写真装置、ならびにイミド化合物
WO2015128779A1 (fr) 2014-02-25 2015-09-03 Basf Se Hétéroacènes pour l'électronique organique
JP6148634B2 (ja) * 2014-03-12 2017-06-14 富士フイルム株式会社 有機半導体結晶の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4678608A (en) * 1985-04-15 1987-07-07 American Cyanamid Company Chemiluminescent composition
US20030111649A1 (en) * 2001-10-22 2003-06-19 Park Koon Ha Chemiluminescent composition for emitting red light
US20080308776A1 (en) * 2007-06-14 2008-12-18 Bindra Perminder S Chemiluminescent compositions and methods of making and using thereof

Also Published As

Publication number Publication date
EP3183757A4 (fr) 2018-04-18
TW201612179A (en) 2016-04-01
TWI680127B (zh) 2019-12-21
CN107004768B (zh) 2020-08-21
CN107074857A (zh) 2017-08-18
TWI693222B (zh) 2020-05-11
KR102417717B1 (ko) 2022-07-07
KR102366484B1 (ko) 2022-02-23
EP3183757A1 (fr) 2017-06-28
JP2017528447A (ja) 2017-09-28
WO2016027218A1 (fr) 2016-02-25
CN107004768A (zh) 2017-08-01
TW201612178A (en) 2016-04-01
US20170237005A1 (en) 2017-08-17
WO2016027217A1 (fr) 2016-02-25
EP3183250A4 (fr) 2018-04-25
JP6861625B2 (ja) 2021-04-21
JP2017532768A (ja) 2017-11-02
US20170250347A1 (en) 2017-08-31
KR20170042358A (ko) 2017-04-18
KR20170042716A (ko) 2017-04-19
EP3183250A1 (fr) 2017-06-28
JP6873034B2 (ja) 2021-05-19
EP3183250B1 (fr) 2023-10-04
US10224485B2 (en) 2019-03-05
US10454037B2 (en) 2019-10-22

Similar Documents

Publication Publication Date Title
EP3183757B1 (fr) Composition à semi-conducteurs organiques comprenant un milieu liquide
EP2297274B1 (fr) Dérivés chlorés d'acide naphtalènetétracarboxylique, leur préparation et leur utilisation dans des dispositifs électroniques organiques
CN103874742B (zh) 咔唑并咔唑-二(二碳酰亚胺)和它们作为半导体的用途
KR101580338B1 (ko) 할로겐-함유 페릴렌테트라카르복실산 유도체 및 이의 용도
US20150179954A1 (en) Substituted terrylene and quaterrylene derivates and use as semiconductors thereof

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170320

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20180315

RIC1 Information provided on ipc code assigned before grant

Ipc: C07D 471/06 20060101ALI20180309BHEP

Ipc: H01L 51/42 20060101ALN20180309BHEP

Ipc: H01L 51/40 20060101AFI20180309BHEP

Ipc: H01L 51/50 20060101ALN20180309BHEP

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MUSIOL, THOMAS

Inventor name: FREYBERG, DIETER

Inventor name: WEITZ, THOMAS

Inventor name: BRILL, JOCHEN

Inventor name: KOEHLER, SILKE ANNIKA

Inventor name: AIZENBERG, ILJA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CLAP CO., LTD.

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20210330

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602015078761

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: H01L0051000000

Ipc: H01L0051540000

RIC1 Information provided on ipc code assigned before grant

Ipc: H01L 51/46 20060101ALI20210714BHEP

Ipc: H01L 51/54 20060101AFI20210714BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20210823

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

INTC Intention to grant announced (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20220103

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1490073

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015078761

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20220504

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1490073

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220504

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220905

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220804

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220805

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220804

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602015078761

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: H01L0051540000

Ipc: H10K0085000000

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220904

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602015078761

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20230207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220817

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220831

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220831

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230828

Year of fee payment: 9

Ref country code: GB

Payment date: 20230831

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230828

Year of fee payment: 9

Ref country code: DE

Payment date: 20230830

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20150817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220504

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602015078761

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20240817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240831